JP2010500397A - Benzimidazole, benzoxazole and benzothiazole derivatives, optical film containing them, and method for producing the same - Google Patents

Abstract

  The present invention relates mainly to the synthesis of planar heterocyclic organic compounds and the production of optical films based on these compounds. The organic compound has a structural formula, wherein Het is hydrophilic and is primarily a planar heterocyclic molecular system; B is a linking group; p is a number in the range of 3 to 8; S is organic A group that confers solubility on the compound; m is a number in the range of 0-8. The organic compound is transparent to electromagnetic radiation in the visible spectral range from 400 to 700 nm. The solution of the compound or salt thereof can also form an essentially transparent optical layer on the substrate, the optical layer having a plane of heterocyclic molecules oriented mainly parallel to the substrate surface. .

Description

  The present invention relates generally to the field of organic chemistry, and more particularly to organic films for displays having phase retardation characteristics.

For the polarization, compensation, and retardation layers or films described in this application, the following term definitions are used throughout the specification and claims.
The term optical axis refers to the direction in which propagating light does not exhibit birefringence.

  Any optically anisotropic medium is characterized by a second-order tensor of its dielectric permittivity. The classification of the compensator plate is clearly related to the orientation of the principal axis of the particular dielectric constant tensor with respect to the natural coordinate frame of the plate. The xyz natural coordinate frame of the plate is chosen so that the z-axis is parallel to the normal direction and the xy plane coincides with the plate surface. FIG. 1 shows an example of the general case where the principal axes (A, B, C) of the dielectric constant tensor are arbitrarily oriented with respect to the xyz frame.

The orientation of the main axis is determined by three Euler angles (θ, φ) that uniquely define different types of optical compensators (FIG. 1) together with the main components of the dielectric constant tensor (ε _A , ε _B , ε _C ). , Ψ). An example where all of the principal components of the dielectric constant tensor have different values corresponds to a biaxial compensator, whereby the plate has two optical axes. For example, if ε _A <ε _B <ε _C , these optical axes are in the plane of the C and A axes on both sides from the C axis. Within one axis range, if ε _A = ε _B , we have a degenerate example if the two axes coincide and the C axis is a single optical axis.

  The zenith angle θ between the C-axis and the z-axis core is very important when defining various compensator types. There are several important types of compensator plates, and in practice it is most often used.

A uniaxial C-plate is defined by Euler angles θ = 0 and ε _A = ε _B ≠ ε _C. In this case, the main C axis (abnormal axis) is perpendicular to the plate surface (xy plane). If ε _A = ε _B <ε _C , the plate is called a “positive C plate”. On the other hand, if ε _A = ε _B > ε _C , the plate is called a “negative C plate”. FIG. 2 shows the orientation of the principal axis of a particular dielectric constant tensor with respect to the natural coordinate frame of positive (a) and negative (b) C plates. The axes OA and OB in the xy plane are equivalent. Therefore, the condition between the refractive index na and the refractive index nb remains fair in the replacement of the index na by the index nb and the replacement of the index nb by the index na.

In general, when the dielectric constant tensor components (ε _A , ε _β , and ε _C ) are complex values, the principal components of the dielectric constant tensor (ε _A , ε _B , and ε _C ), the refractive index (na, nb, And nc), and absorption coefficients (ka, kb and kc) satisfy the following conditions:
na = Re [(ε _A ) ^1/2 ], nb = Re [(ε _B ) ^1/2 ], nc = Re [(ε _C ) ^1/2 ], ka = lm [(ε _A ) ^1/2 ], Kb = lm [(ε _B ) ^1/2 ], kc = lm [(ε _C ) ^1/2 ].

Liquid crystals are widely used in electronic display devices. In such display systems, the liquid crystal cell is typically located between a pair of polarizer and analyzer plates. Incident light is polarized by the polarizer and propagates through the liquid crystal cell. In this liquid crystal cell, the propagation of incident light is affected by the molecular orientation of the liquid crystal controlled by applying a bias voltage across the cell. Thereafter, the changing light is propagated through the analyzer. By employing this scheme, the transmission of light from any external source including ambient light can be controlled. The energy required to do this control is generally much lower than the energy required to control light emission from a luminescent material used in a display type such as a cathode ray tube (CRT). Accordingly, liquid crystal technology is used in many electronic imaging devices where light weight, low power consumption, and long service life are important, including but not limited to digital watches, calculators, portable A computer and an electronic game machine are mentioned.

  Contrast, color reproduction, and stable gray scale intensity are important quality characteristics of electronic displays using liquid crystal technology. A major factor determining the contrast of a liquid crystal display (LCD) is the tendency of light to “leak” by liquid crystal molecules or cells in a dark or “black” pixel state. Furthermore, the optical leakage and thereby the contrast of the LCD also depends on the direction in which the display screen is viewed. Typically, the optimal contrast is observed only within a narrow viewing angle range centered on the normal to the display (α = 0) and decreases rapidly as the polar viewing angle α is increased. FIG. 3 shows the definition of the viewing angle direction. In color displays, the leakage problem not only degrades contrast but also causes color or hue shifts as well as degradation of color reproduction.

  LCDs are televisions (TVs), computers (such as notebook computers or desktop computers), central controllers, and various devices, such as gambling equipment, electro-optic displays (such as watches, pocket calculators, pocket electronics, etc.) Game) and a portable data bank (for example, a portable information terminal or a mobile phone), the monitor is replaced with a CRT. It is expected that the number of LCD TV monitors with larger screen sizes will increase rapidly in the future. However, LCD applications as a replacement for traditional CRT are limited unless the problems affected by viewing angles such as coloring, contrast degradation, and brightness reversal are resolved.

  In a normally white display configuration, a 90 ° twisted nematic cell is placed between crossed polarizers so that the transmission axis of each polarizer is the orientation vector of the liquid crystal molecules ( It is parallel to the orientation of the director. This reverses the sense of the bright and dark areas compared to the normally black display. In a normally white display, the unapplied (unbiased) area appears bright, while the applied area appears dark. The problem of dark areas on the surface that appear bright when viewed at large angles still arises. However, the reason is different and the correction requires different types of optical compensation elements. In the applied region, the liquid crystal molecules tend to align in the direction of the applied electric field. If this alignment is perfect, all the liquid crystal molecules in the cell are considered to have a long axis perpendicular to the substrate glass plate. This arrangement, known as a homeotropic arrangement, shows the optical symmetry of a positive birefringence C-plate. In the energized state, normally white is isotropic to normal incident light blocked by crossed polarizers.

Loss of contrast occurs as the viewing angle increases. This is because the homeotropic liquid crystal layer is not isotropic to light propagating at an angle with respect to the normal direction. Light directed to a non-zero angle relative to the normal propagates in two modes due to the birefringence of the layer, and the phase delay between these modes increases with the light incident angle. This phase dependence on the angle of incidence introduces ellipticity into the polarization state and then disappears incompletely by the second polarizer, causing light leakage. Birefringence does not depend on the azimuth angle because of C-plate symmetry. Obviously, what is needed is an optical compensator and is C-plate symmetric but has negative birefringence. Such a compensator would cause a phase delay that is opposite in sign to that produced by the liquid crystal layer, thereby restoring the original polarization state and allowing light to be blocked by the output polarizer.

  No method was available to stretch or compress the polymer to obtain a large area film with negative C-plate optical symmetry and the required uniformity. Further, it has not been possible to form a compensation plate from a negative birefringent crystal such as sapphire. In order for such a compensator to be effective, the phase delay of such a plate must be similar to that in liquid crystal and must vary with visual angle at the same rate as the phase delay in liquid crystal. It is thought that it must be done. These constraints suggest that the thickness of the negative C plate will be about 10 μm, making it very difficult to perform such an approach. Because it will ensure that the surface of the plate is parallel, it will require polishing of a thin plate with very accurate birefringence (negative). Since the size of such a display is relatively large, the effectiveness of a sufficiently sized negative birefringence would be a further challenge.

  One type of C plate is known, and the C plate is composed of alternating thin films of materials having different reflectivities. Such a layer structure operates as an artificial birefringent thin plate. The multilayer compensator made in this way can exhibit negative birefringence. Furthermore, the desired birefringence of the multilayer structure can be precisely adjusted by choosing an appropriate layer thickness and material. The main drawback of the C plate is its high production cost.

  Uncompensated full color LCDs typically show a large change in chromaticity over the field of view. Thus, a region that exhibits one color when viewed at normal incidence may exhibit low saturation or may appear as its complementary color when viewed at a large angle. These are due to the same physical mechanism that causes a decrease in contrast at large angles, ie unnecessary light leakage due to dark areas on the surface.

US Pat. No. 5,315,129 US Pat. No. 6,451,415 US Pat. No. 5,315,129 US Pat. No. 5,739,296 US Pat. No. 6,049,428

L. Scuderoo et al., “A Self-Organized Two-Dimensional Biological Structure”, J. Am. Phys. Chem. B, 107, 2903-2909 (2003) X. Fan, J. Rocklin, J. Ho York et al. (X. Fan, J. Locklin, J. Ho Yuk, et al.), “Nanostructured Sexithiophene / Cray Hybrid Multilayers”, A Comparative Chem. Mater. 14: 2184-2191 (2002) P. Lazarev et al., “X-ray Diffraction by Large Area Organic Crystalline Nanofilms”, Molecular Materials, 14 (4), 303-311. Y. Bobrov, “Special Properties of Thin Crystal Film Polarizers”, Molecular Materials, 14 (3), 191-203 (2001) James A. Theobald et al., “Controlling Molecular Deposition and Layer Structure with Supramolecular Surface, 29th, 10th, 29th, 10th, 29th, 10th, 29th, 10th, 29th, 10th, 29th, 10th. Luckinger et al., “Langmuir”, Vol. 21, pages 4984-4988 (2005). R. Centore and A. Tuzi, “Crystal Eng.”, Vol. 6, pages 87-97 (2003) Reddy et al., “Crystal Growth & Design”, Volume 4, pages 89-94 (2004). Jayaraman et al. “Crystal Growth & Design”, Vol. 4, pages 1403-1409 (2004) Dee Lynch et al., “Crystal Eng.”, Vol. 2, pages 137-144 (1999)

  The present invention provides a practical solution to the need for such a compensator. The aim is to produce crystalline retarder films with high optical parameters on organic compounds. Generation of such types of crystalline retarders requires that the molecules in the multilayer film be specially arranged. Organic molecules must be parallel to the surface on the substrate.

  There is a known organic pseudo-epitaxial method intended for the formation of optoelectronic devices (see Patent Document 1). According to this method, the plane of the organic molecule is oriented parallel to the surface on the substrate. The pseudo-epitaxial optoelectronic device structure includes a substrate, a first layer placed on the substrate, and a second layer placed on the first layer. The first layer represents a planar crystalline film of an organic aromatic semiconductor composite. It is selected from the list of organic compounds including polyacene, porphyrin and their derivatives. The second layer further represents a planar crystal film of an organic aromatic semiconductor. Its chemical composition (generally different from that of the first layer) is also selected from a list of organic compounds including polyacene, porphyrin, and derivatives thereof. The first and second layers have a crystalline structure, and they are in a certain correlation with each other. The first and second layers are in particular composed of 3,4,9,10-perylenetetracarboxylic dianhydride (PTCDA), 3,4,7,8-naphthalenetetracarboxylic dianhydride (NTCDA), copper It can be independently selected from a list comprising phthalocyanine, 3,4,9,10-perylenetetracarboxylic acid bis-benzimidazole, and -oxadiazole derivatives. Organic optoelectronic devices have been grown by using organic molecular beam deposition techniques. Using an organic molecular beam deposition method, the organic material was deposited as an extremely thin layer by 10 angstroms (A).

PTCDA and NTCDA have been confirmed to be excellent materials for producing organic optical IC devices. However, any planar type aromatic organic semiconductor that can easily form a crystal structure may be used. The preferred method of the prior art uses a chamber containing an inorganic substrate made of a suitable material to make electrical contacts to PTCDA and NTCDA sources and organic structures. The chamber pressure is generally maintained below 10 ⁻⁶ Torr. The substrate and the source of the component material are arranged with a certain minimum separation distance of 10 cm. During deposition, the substrate temperature is kept below 150K while the PTCDA and NTCDA sources are selectively heated.

  Despite all the advantages of the pseudo-epitaxial growth method (see Patent Document 2 and Patent Document 3), it is not without inconvenience. According to the known method, a constant temperature control and vacuum level must be maintained in the chamber throughout the epitaxial growth process. Any breakdown during temperature and vacuum control will lead to the appearance of defects in the growing layer, so both the crystallographic parameters and the orientation of the molecular layer show a change. Such process sensitivity in terms of technical parameter instability can also be regarded as a problem with the known method, which is particularly important in the deposition of relatively thick (1-10 μm) epitaxial layers. .

Another problem with the method is that it requires sophisticated technical equipment. The reactor chamber must maintain ultra high vacuum (10 ⁻⁶ to 10 ⁻¹⁰ Torr) and must withstand significant temperature gradients between closely spaced areas. The apparatus must have means for heating the source and means for cooling the substrate, a complex pumping stage, and equipment for gas addition, temperature and pressure monitoring, and technical process control. Don't be. High vacuum requirements make the process expensive and limit the dimensions of the substrate.

  Another problem with the known techniques is the limitation on the choice of substrate material: under conditions of large pressure differentials, high vacuum, and significant temperature gradients, their physical, mechanical, optical, and other Only substances that retain these properties can be used.

  The production of two-dimensional bimolecular surface structures was demonstrated using weak non-covalent interactions, and the product was characterized by scanning tunneling microscopy (see Non-Patent Document 1). This work closely follows the idea of three-dimensional crystal engineering. Thereby, the concept of supramolecular reactants (synthons) is applied to molecular systems that are suppressed in two dimensions by physical adsorption (physical adsorption) on a conductive surface. An ordered planar structure that self-assembles by fluorine-phenyl interaction was demonstrated. This study provides an example of systematic design of self-organized layers. Fully fluorinated cobalt phthalocyanine (F16CoPc) film thermally deposited on gold includes reflection absorption infrared spectroscopy (RAIRS), X-ray and ultraviolet photoelectron spectroscopy (XPS and UPS), and scanning tunneling microscopy (STW). And was characterized by UPS spectra of thin films of CoPc, F16CoPc and nickel tetraphenylporphyrin (NiTPP) on gold were measured. Their relative surface charges were also compared. STM images of monolayers of F16CoPc, NiTPP, and a mixture of NiTPP-F16CoPc and NiTPP-CoPc were obtained. It was found that the ordered 1: 1 structure was spontaneously formed by NiTPP-FI6CoPc, while NiTPP-CoPc formed a two-dimensional solid solution.

There is a growing interest in ultra-thin films prepared from certain inorganic and organic materials as hybrid nanocomposite materials. Formation of a nanostructured ultrathin film composed of montmorillonite clay (MONT) and a bicarbonate sexithiophene derivative (6TN) was studied using a multilayer self-assembly method (see Non-Patent Document 2). The main objective was to study the structure and layer order in these films suitable for future applications in organic semiconductor devices. The structure and morphology of 6TN / MONT multilayers prepared from pure water and 0.1 M NaCl system are compared. The 6TN amphiphile showed a unique aggregation behavior that was altered in the presence of salt and THF as co-solvents both in solution and on the surface. On the clay surface, 6TN agglomerates deposited from saline showed a more uniform particle size distribution and adsorption rate than those obtained from the pure water system. This was confirmed by UV-VIS spectrum, X-ray diffraction (XRD), and atomic force microscope (AFM). The idea of incorporating more 6TN species adsorbed on the surface so that a smoother surface morphology is obtained must have significant implications for semiconductor device assembly.

  The available literature does not present an example of a film with a vertical orientation of a stack prepared by a low cost and effective method for applying a solution on a substrate. By using a lyotropic liquid crystal (LLC) solution of a sulfo derivative, a film having a horizontally aligned stack is generally obtained (see Patent Document 4 and Patent Document 5, and Non-Patent Document 3 and Non-Patent Document 4).

  On the other hand, the literature shows that some molecules can form regularly arranged planar fragments (supermolecules) of the surface on the substrate that are precipitated from solution in water and various organic solvents, As well as hydrogen bonds H bonds are the driving force for the formation of such planar supramolecules. This phenomenon was observed for heterocyclic amines, amides, and carboxylic acids. The type of monolayer structure obtained depends on the molecular structure, solvent, and surface activity. Different types of layer structures (stable and unstable, dense and relaxed) can be obtained using different molecular structures and conditions.

  There are many novel adsorbate-substrate systems, which are known to exhibit a high degree of large-scale ordering. Scanning tunneling microscopy (STM) has been found to be able to study the electronic properties of such systems and structures at submolecular resolution levels. In some systems, it has been established that H-bonds are the dominant interactions between molecules or govern the molecular assembly process.

  Selective non-covalent interactions have been widely used in solution chemistry to assemble molecules into nanometer-sized functional structures such as capsules, switches, and prototype nanomachines. The concept of supramolecular construction has also been applied to two-dimensional (2D) assemblies on the surface stabilized by H-bonds, dipole bonds, or metal coordination. Another way to control the surface structure is to use a monolayer of adsorbed molecules to create selective binding sites that provide individual target molecules. James A. Theobald et al. (5) combine these methods using H-bonds to assemble an assembly of two types of molecules into an open beehive 2D network. Led to structure. This network structure controls the new surface phase formed by the subsequently deposited fullerene molecules and creates its template. It has been found that the open network structure acts as a 2D array of large pores with sufficient capacity to provide several large guest molecules, serving as a template for forming ordered fullerene layers.

Self-assembly of a loosely packed H-bonded 2D network structure of trimesic acid (TMA) at the liquid-solid interface was observed using STM (see Non-Patent Document 6). Two crystallographically different 2D phases of TMA were identified and selected by changing the solvent. In this paper, several models of various crystal structures with corresponding H-bonding modes were introduced. (A) wire mesh structure, a = b = 1.7 nm, angle σ = 60 °, area = 2.5 nm ² , 2 molecules / unit cell; (b) flower structure, a = b = 2.5 nm, angle σ = 60 °, area = 5.4 nm ² , 6 molecules / unit cell; (c) based on a completely triple H bond, representing a more densely packed 2D-TMA polymorph "Flower" structure. It was suggested that the denser “flower” structure (b) would be the most thermodynamically stable of the two single-layer polymorphs observed. Studies on these adsorbed polymorphic structures of TMA dissolved in a series of acid solvents [CH ₃ (CH ₂ ) _n COOH where n = 2-7] show that the flower structure is preferred for shorter chain solvents and that TMA The solubility was maximized. It should be noted that a purely tripled H-bond structure (a “super flower” structure) may have been able to make an even more densely packed TMA structure. However, this TMA form was not observed. A possible interpretation of this behavior is that in short-chain solvents, TMA trimer [(TMA) ₃ ] solution phase nucleating species, which are considered TMA flower-form precursors, are stabilized. However, the explanation based on the difference in solvent stabilization of the surface monolayer of the flower structure and the wire mesh structure cannot be excluded.

Crystal packing of several fluorinated azobenzene carboxylic acids has been studied by R. Centore and A. Tuzi (7). _{C 6 H 5 COOH, C 6} F 5 COOH (1), X -ray of _{C 6 H 5 CONH 2, C} 6 F 5 CONH 2 (2) and _{C 6 H 5 CONH 2, C} 6 F 5 COOH (3) Were analyzed to elucidate the role of Ph-PhF synthons in inducing self-assembly and H-bonding in these co-crystals (see Non-Patent Document 8). The high acidity of the C ₆ F ₅ COOH and C ₆ F ₅ CONH ₂ H-bond donors with a mixed stack of phenyl and perfluorophenyl rings allows interacid and interamide in co-crystals 1 and 2 H bonds are provided. The acid amide H bond is sufficiently strengthened by a donor acidity and acceptor basicity of 3, so the role of the Ph-PhF synthon is weaker because the aromatic rings are stacked with side offsets. Under similar crystallization conditions, complex C ₆ H ₅ COOH, C ₆ F ₅ CONH ₂ (4) could not be obtained. The crystal structure of C ₆ F ₅ CONH ₂ was also determined in order to compare the molecular organization and H bonds with the motif in the co-crystal.

  It was found that 4-hydroxybenzoic acid (1) crystallized into three crystal forms. (I) monoclinic from DMSO solution (1A), (ii) triclinic from solution in 1: 1 DMSO / heated ethyl acetate (1B), and (iii) from pyridine solution (1C) It is triclinic (see Non-Patent Document 9). A rational explanation for the formation of these pseudopolymorphs and the structural similarity of their filling motifs can be given in terms of fractional multipoint solute-solvent interactions. In all three structures, crystallographic aspects related to the influence of solvent molecules on the formation of H-bonded network structures are described. In addition to strong H bonds, C—H... O, C—H... Π, and π.

  A series of 4,4-dipyridyl (4,4-DP) derivatives were prepared and investigated using single crystal X-ray diffraction techniques (see Non-Patent Document 10). The structure increased complexity in the overall H-bond network. One structure contains a polymer H-bonded chain of 4,4-DP and ICA-associated molecules that propagate through complementary sites on the ICA molecule. The structure of 2 consists of two polymer H-bonded chains in parallel, each chain with 4,4-DP and 3-ABA associated molecules bridged through complementary 3-ABA sites. The structure of 3 was an extensive three-dimensional H-bond network for all H-bond donor and acceptor sites on the constituent molecules. In each case, the location and orientation of the N—H group was important in determining the final lattice network.

As mentioned above, in the most common example, a biaxial film is characterized by three different principal values of refractive index n _A , n _B , n _C , and an experiment in which the xy plane coincides with the optical film plane. The main axes A, B, and C are arbitrarily oriented with respect to the xyz frame. Hereinafter, the present invention will be described using an important specific example in which the main axes are oriented in the following forms: A || x; B || y; C || z.
The present invention uses in-plane H bonds applied to predominantly planar heterocyclic molecular systems containing nitrogen heteroatoms to form an ordered planar structure. This idea was checked for heterocyclic compounds substituted with acid residues. Experiments have confirmed the possibility of obtaining films with desirable optical properties.

  In a first aspect of the invention, an organic compound of structural formula (I) is provided.

Where Het is a predominantly planar heterocyclic molecular system with hydrophilicity; B is a linking group; p is 3, 4, 5, 6, 7, or 8; S is an organic compound M is 0, 1, 2, 3, 4, 5, 6, 7, or 8. Organic compounds are transparent to electromagnetic radiation in the visible spectral range from 400 to 700 nm. The solution of the compound or salt thereof can also form an essentially transparent optical layer on the substrate, the optical layer having a plane of heterocyclic molecules oriented mainly parallel to the substrate surface. .
According to a second aspect of the present invention, there is provided an optical film comprising a substrate having a front surface and a back surface, and at least one solid layer on the substrate, wherein the solid layer includes at least one organic compound of the structural formula (III). provide.

Where Het is a predominantly planar heterocyclic molecular system with hydrophilicity; B is a linking group; p is 3, 4, 5, 6, 7, or 8; S is an organic compound M is 0, 1, 2, 3, 4, 5, 6, 7, or 8; X is H ⁺ , NH ₄ ⁺ , NH (C ₂ H _g ) ₃ ⁺ , NH (CH ₃ ) ₃ ⁺ , NH (C ₃ H ₇ ) ₃ ⁺ , Na ⁺ , K ⁺ , Li ⁺ , Cs ⁺ , Ba ²⁺ , Ca ²⁺ , Mg ²⁺ , Sr ²⁺ , La ³⁺ , Zn ²⁺ , Zr ⁴⁺ , Ce ³ , Y ³⁺ , Yb ³⁺ , Gd ³⁺ and counterions from a list comprising any combination thereof; t is the number of counterions of a given organic compound. The plane of the heterocyclic molecule is oriented mainly parallel to the surface of the substrate, and the solid layer acid is transparent to electromagnetic radiation in the visible spectral range from 400 to 700 nm. The solid layer is preferably on the front surface of the substrate.

  A third aspect of the present invention provides a method for producing an optical film, the method comprising several steps. The first step is to prepare a solution of an organic compound of structural formula (I) or a salt thereof.

  Where Het is a hydrophilic, predominantly planar heterocyclic molecular system; B is a linking group; p is 3, 4, 5, 6, 7, or 8; S is an organic compound M is 0, 1, 2, 3, 4, 5, 6, 7, or 8. At least some of the heterocyclic molecular systems are capable of horizontally forming non-equal particles in solution, resulting from the interaction of the side of the linking group by non-covalent chemical bonding. The second step is to apply a liquid layer of a solution of the organic compound on the substrate. The liquid layer is substantially transparent to electromagnetic radiation in the visible spectral range from 400 to 700 nm. Flat non-equal particles of a heterocyclic molecular system are bonded to each other and mainly oriented on the plane of the substrate due to the interaction of the side of the bonding group due to non-covalent chemical bonding. To do. The final step is drying with the formation of a solid layer.

  In a fourth aspect of the invention, a method for synthesizing a 2,2'-bibenzheteroazole derivative represented by Structural Formula (IV) is provided:

Where q + l = 0, 1, 2, 3 or 4; q ′ + I ′ = 0, 1, 2, 3 or 4; the E and G parts are independent of the list containing O, S, NR ⁴ R ⁴ is independently selected from the list comprising H, NH ₂ , OH; R ⁵ , R ′ ⁵ , R ⁶ and R ′ ⁶ are —COOH, —COMe, —CO ₂ Me , —CONH ₂ , —CONHNH ₂ , —SO ₃ H, —SO ₂ NH ₂ , —SO ₂ —NH—SO ₂ —NH ₂ , the method comprises the following steps:
a) reacting a component of formula (V) with a component selected from a list comprising structures (VII) and (VIII);
b) reacting the compound obtained in the previous step with a component of formula (VI);

Here, the solvent is selected from a list comprising AcOH, DMF, MeOH, EtOH, and mixtures thereof.
A fifth aspect of the invention provides a method for synthesizing 2,2′-bibenzheteroazole derivatives represented by structural formula (IV ′):

Where q + 1 = 0, 1, 2, 3 or 4; the E moiety is selected from a list containing O, S, NR ⁴ where R ⁴ is selected from a list containing H, NH ₂ , OH. R ⁵ and R ⁶ represent —COOH, —COMe, —CO ₂ Me, —CONH ₂ , —CONHNH ₂ , —SO ₃ H, —SO ₂ NH ₂ , —SO ₂ —NH—SO ₂ —NH ₂ ; Selected independently from the containing list, the method includes the following steps:
a) reacting a component of formula (V) with a component selected from the list comprising structures (VII) and (VIII); and

(B) stirring the mixture;
Here, the solvent is selected from a list comprising AcOH, DMF, MeOH, EtOH, and mixtures thereof.

  In one embodiment, the molar amount of the component of formula (V) is included in the reaction mixture twice compared to the molar amount of the compound selected from the list comprising structures (VII) and (VIII).

In one embodiment, the method includes treating the mixture with Et ₃ N and then with HCl, wherein the operation of the treatment occurs at or after the agitation step.
The sixth aspect of the present invention provides a 2,2′-bibenzheteroazole derivative of structural formula (IV).

Where q + l = 0, 1, 2, 3 or 4; q ′ + I ′ = 0, 1, 2, 3 or 4; the E and G parts are independent of the list containing O, S, NR ⁴ R ⁴ is selected from a list comprising H, NH ₂ , OH; R ⁵ , R ′ ⁵ , R ⁶ and R ′ ⁶ are —COOH, —COMe, —CO ₂ Me, —CONH _{2, -CONHNH 2, -SO 3 H} , are selected independently from the list comprising _-SO 2 NH _2, and _{-SO 2 -NH-SO 2 -NH 2} .

  In a seventh aspect of the present invention, tricarboxy-5,11,17-trimethyl-11,17-dihydro-5H-bisbenzidiimidazo represented by the structural formula (IX) [1 ′, 2 ′: 3,4 1 ″, 2 ″: 5,6] [1,3,5] triazino [1,2-a] benzimidazole-6,12,18-triium bromide.

This method includes the following steps:
a) Bromination and methylation of 1H-benzimidazole-6-carboxylic acid, and b) of 2-bromo-1-methyl-1H-benzimidazole-5 (6) -carboxylic acid obtained in step (a). Condensation.

  The eighth aspect of the present invention is the bisbenzimide azo [1 ′, 2 ′: 3, 4; 1 ″, 2 ″: 5, 6] [1, 3, 5] represented by the structural formula (X). A method of synthesizing triazino [1,2-a] benzimidazole-tricarboxylic acid is provided.

The method includes the following steps:
a) Preparation of methyl 3,4-diaminobenzoate dihydrochloride comprising bubbling hydrogen chloride through a solution of 3,4-diaminobenzoic acid in methanol;
b) preparing methyl 2-oxo-2,3-dihydro-1H-benzimidazole-5-carboxylate by condensation of methyl 3,4-diaminobenzoate dihydrochloride from step (a) with urea. ;
c) Methyl 2-oxo-2,3-dihydro-1H-benzimidazole-5-carboxylate from step (b) was converted to methyl 2-chloro-1H-benzimidazole- by treatment with hydrogen chloride and phosphorus oxychloride. Converting to 5 (6) -carboxylate;
d) Trimerization of the methyl 2-chloro-1H-benzimidazole-5 (6) -carboxylate obtained from step (c) by trimethylbisbenzimidazo [1 ′, 2 ′: 3,4]; 1 ", 2": 5,6] [1,3,5] triazino [1,2-a] benzimidazole tricarboxylate; and e) trimethylbisbenzimidazo [1] from step (d) ', 2': 3, 4; 1 "
, 2 ″: 5,6] [1,3,5] triazino [1,2-a] benzimidazole tricarboxylate by alkaline hydrolysis to obtain product (X).

  Having outlined the invention, a better understanding can be gained by reference to certain preferred embodiments. The embodiments herein are for illustrative purposes only and are not intended to limit the scope of the appended claims.

The present invention relates to the production of organic compounds suitable for producing optical films whose molecular planes are mainly oriented parallel to the surface of the substrate.
Preferably, the structures of the disclosed organic compounds are characterized by heteroatoms, COO ⁻ , SO ₃ ⁻ , HPO ₃ ⁻ , PO ₃ ²⁻ , NH, NH ₂ , CO, OH, NHR, NR, COOMe, The presence of three or more linking groups selected from the list comprising CONH ₂ , CONHNH ₂ , SO ₂ NH ₂ , —SO ₂ —NH—SO ₂ —NH ₂ , and any combination thereof, wherein The radical R is an alkyl or aryl that allows for lateral H-bonding of the heterocyclic molecule and allows for an aggregate formed from one another that tends to form planar H-bonded supramolecules. Preferred alkyl and aryl groups are listed below.
Alkyl group:
General formula: C _n H _{2n + 1} —, where n is 1 to 23, preferably 1, 2, 3, or 4
Examples: methyl (CH ₃ —), ethyl (C ₂ H ₅ —), propyl (CH ₃ CH ₂ CH ₂ — or CH ₃ CH (CH ₃ ) —), butyl (CH ₃ CH ₂ CH ₂ CH ₂ — or C (CH ₃ ) ₃ — or CH ₃ CH ₂ CH (CH ₃ ) — or CH ₃ CH (CH ₃ ) CH ₂ —)
Aryl group:
Example: a phenyl group _{(C 6 H} 5 -), benzyl _{(C 7 H 7} -), naphthyl _(C 10 _H 7 -)
The acid groups provide physisorption of selected heterocyclic compounds on various substrates, including those made of carbon, diamond, gold, silver, glass, and many other materials. The interaction of the H-bonded system formed by the linking groups in the planar supramolecule with the hydrophilic surface can cause in-plane orientation of the supramolecule. The hydrophilic surface and planar H-bonded supramolecules form a layer on the substrate surface.

The arrangement of acid groups affects the structure of planar H-bonded supramolecules and may produce various structural motifs with different spatial configurations.
Organic compounds of structural formula (I) can be prepared using conventional methods known in the art. Some heterocyclic compounds can be synthesized by cyclization of a fragment having a carboxylic acid group, or by introducing a substituent into a commercially available heterocyclic system and post-modifying them.

In order to obtain an optical film comprising planar H-bonded heterocyclic molecules oriented parallel to the substrate, it is preferable to provide two types of interactions in this system. That is,
The first factor is the interaction (adsorption) of planar heterocyclic molecules (adsorbents) on the substrate (adsorbent) resulting in the desired orientation of the molecules on the surface of the substrate or their aggregates. Molecular adsorption is either physical (physical sorption) or chemical (chemical adsorption). Intermolecular force is present in physical adsorption, and the electronic structure of the adsorbed molecule does not change significantly. In this case, the adsorbed molecule (adsorbed molecule) usually maintains the surface (side surface) mobility. Chemisorption involves the formation of chemical bonds between adsorbate molecules and adsorbent molecules. Therefore, chemisorption can be regarded as one of chemical reactions in a region limited to the surface layer of the adsorbate. Obviously, chemical bonding limits the surface mobility of adsorbed molecules. The disclosed invention uses a combination of an organic compound (adsorbate) featuring mainly physical adsorption and a substrate. Thus, adsorbed molecules and their aggregates can migrate onto the surface on the substrate.

Next, physically adsorbed planar heterocyclic molecules should interact with each other by weak lateral forces acting in the substrate plane. These intermolecular forces play an important role in the formation of long-range order in the adsorption layer and the final monolayer. Lateral interactions can be provided by H bonds formed between several substitutions of the heterocyclic molecule.

In one embodiment of the organic compound according to the invention, the predominantly planar heterocyclic molecular system is partially or fully conjugated. In another embodiment of the organic compound according to the present invention, the heterocyclic molecular system comprises a heteroatom selected from the list comprising nitrogen, oxygen, sulfur, and any combination thereof. In one embodiment of the organic compound according to the present invention, at least one of the bonding groups is the heteroatom, COOH, SO ₃ H, H ₂ PO ₃ , NH, NH ₂ , CO, OH, NHR, NR, COOMe, CONH _{2, CONHNH 2, sO 2 NH} 2, selected from the list comprising _{-SO 2 -NH-sO 2 -NH 2} , and any combination thereof, as described above, the radical R in the formula is an alkyl or aryl . In yet another embodiment of the disclosed organic compound, at least one of the linking groups is a complementary group. Identical linking groups belonging to different heterocyclic molecular systems can also form non-covalent chemical bonds between these systems. Such linking groups are called self-bonding or complementary. In another embodiment of the organic compound according to the invention, at least one of the linking groups is selected from a list comprising a hydrogen acceptor (A), a hydrogen donor (D), and a group having the structural formula (II).

In the formula, the hydrogen acceptor (A) and the hydrogen donor (D) are independently selected from the list containing NH groups and oxygen (O).
In one embodiment of the disclosed invention, the organic compound further ensures absorption of electromagnetic radiation within at least one predetermined sub-range of the UV spectral range.

In another embodiment of the disclosed invention, at least one of the linking groups acts as a group that provides solubility of the organic compound in water or in an organic solvent. The group S that confers solubility of organic compounds in water may be selected from the list consisting of COOH, SO ₃ H, H ₂ PO ₃ , and any combination thereof. The group S conferring the solubility of the heterocyclic molecular system in an organic solvent may be selected from the list consisting of CONR ¹ R ² , CONHCONH ₂ , SO ₂ NR ¹ R ² , R ³ , or any combination thereof. . Here, as defined above, R ¹ , R ² and R ³ are selected from hydrogen, alkyl, and aryl.

In one embodiment of the disclosed invention, the heterocyclic molecular system has an expanded anisoaxial form with a longitudinal axis. In another embodiment of the disclosed invention, the heterocyclic molecular system has an axis of symmetry of order k (C _k ) perpendicular to the plane of the heterocyclic molecular system, where k is It is an integer of 3 or more. Examples of predominantly planar heterocyclic molecular systems with pyrazine and / or imidazole fragments having the structural formula are shown in Table 1.

  Table 1. Examples of predominantly planar heterocyclic molecular systems with pyrazine and / or imidazole fragments

In one embodiment of the organic compound, the heterocyclic molecular system (Het) has the structural formula shown in Table 2. The E and G moieties are independently selected from a list containing O, S, NR ⁴ (where R ⁴ is selected from a list containing H, NH ₂ , OH):
Table 2. Example of predominantly planar heterocyclic molecular system with expanded anisoaxial morphology

  In one embodiment of the organic compound, the heterocyclic molecular system is an oligomer comprising imidazole and / or benzimidazole cycle, or any of them, which can form hydrogen bonds. Examples of predominantly linear heterocyclic systems with oligomers containing the imidazole and benzimidazole cycle having the structural formula, or either are shown in Table 3. Here, n is a number within the range of 1-5.

  Table 3. Examples of heterocyclic molecular systems containing oligomers containing imidazole and benzimidazole cycles, or either

本発明の別の実施形態では、１Ｈ，１’Ｈ−２，２’−ビベンズイミダゾールの誘導体、２，２’−ビ−１，３−ベンゾキサゾールの誘導体、および２，２’−ビ−１，３−ベンゾキサゾールの誘導体を含むリストから選択される。また本発明のさらに別の実施形態では、有機化合物には表４に示される構造式を有する。

In another embodiment of the invention, a derivative of 1H, 1′H-2,2′-bibenzimidazole, a derivative of 2,2′-bi-1,3-benzoxazole, and 2,2′-bibenz Selected from the list comprising derivatives of -1,3-benzoxazole. In yet another embodiment of the invention, the organic compound has the structural formula shown in Table 4.

  Table 4.2.2 Examples of 2'-bibenzimidazole derivatives

有機化合物の別の実施形態では、結合基は、非共有結合の化学的結合によって溶液でのフラットな非等軸粒子の形成をもたらす。有機化合物のさらに別の実施形態では、非共有結合の化学結合は、単水素結合、双極子間相互作用、陽イオン−パイ相互作用、ファンデルワールス相互作用、配位結合、イオン結合、イオン双極子相互作用、多重水素結合、ヘテロ原子を介した相互作用、およびそれらの任意の組み合わせを含むリストから選択される。また有機化合物の別の実施形態では、少なくとも１つの結合基は、溶液内の非等軸粒子の不安定な平衡を与える。本発明の一実施形態では、有機化合物は、−ＣＨ_３、−Ｃ_２Ｈ_５、−ＮＯ_２、−Ｃｌ、−Ｂｒ、−Ｆ、−ＣＦ_３、−ＣＮ、−ＮＣＳ、−ＯＨ、−ＯＣＨ_３、−ＯＣ_２Ｈ_５、−ＯＣＯＣＨ_３、−ＯＣＮ、−ＳＣＮ、−ＮＨ_２、−ＮＨＣＯＣＨ_３、および−ＣＯＮＨ_２を含むリストから選択される少なくとも１つの追加の置換基をさらに含む。
本発明はまた、上記に開示されたように、光学フィルを提供する。開示された光学フィルムの一実施形態では、主に平面のヘテロ環式分子系は、部分的あるいは完全に共役したものになる。開示された光学フィルムの別の実施形態では、前記ヘテロ環式分子系は、窒素、酸素、硫黄、およびそれらの任意の組み合わせを含むリストから選択されるヘテロ原子を含む。開示された光学フィルムのさらに別の実施形態では、少なくとも１つの結合基は、水素受容体（Ａ）、水素供与体（Ｄ）、および構造式（ＩＩ）を有する基を含むリストから選ばれる。

In another embodiment of the organic compound, the linking group results in the formation of flat non-equal particles in solution by non-covalent chemical bonding. In yet another embodiment of the organic compound, the non-covalent chemical bond is a single hydrogen bond, dipole interaction, cation-pi interaction, van der Waals interaction, coordination bond, ionic bond, ionic dipole. It is selected from a list that includes child interactions, multiple hydrogen bonds, interactions through heteroatoms, and any combination thereof. In another embodiment of the organic compound, the at least one linking group provides an unstable equilibrium of the non-equal axis particles in solution. In one embodiment of the present invention, organic _{compounds, -CH 3, -C 2 H 5} , -NO 2, -Cl, -Br, -F, -CF 3, -CN, -NCS, -OH, -OCH Further comprising at least one additional substituent selected from a list comprising: ₃ , —OC ₂ H ₅ , —OCOCH ₃ , —OCN, —SCN, —NH ₂ , —NHCOCH ₃ , and —CONH ₂ .
The present invention also provides an optical fill as disclosed above. In one embodiment of the disclosed optical film, the predominantly planar heterocyclic molecular system is partially or fully conjugated. In another embodiment of the disclosed optical film, the heterocyclic molecular system comprises a heteroatom selected from the list comprising nitrogen, oxygen, sulfur, and any combination thereof. In yet another embodiment of the disclosed optical film, the at least one linking group is selected from a list comprising a hydrogen acceptor (A), a hydrogen donor (D), and a group having the structural formula (II).

式中、水素受容体（Ａ）および水素供与体（Ｄ）は、ＮＨ基および酸素（Ｏ）を含むリストから独立して選ばれる。開示された光学フィルムの一実施形態では、結合基は、前記ヘテロ原子、ＣＯＯＨ、ＳＯ_３Ｈ、Ｈ_２ＰＯ_３、ＮＨ、ＮＨ_２、ＣＯ、ＯＨ、ＮＨＲ、ＮＲ、ＣＯＯＭｅ、ＣＯＮＨ_２、ＣＯＮＨＮＨ_２、ＳＯ_２ＮＨ_２、−ＳＯ_２−ＮＨ−ＳＯ_２−ＮＨ_２、およびそれらの任意の組み合わせを含むリストから選択され、上記したように、式中ラジカルＲはアルキルまたはアリールである。開示された光学フィルムの別の実施形態では、少なくとも１つの結合基は相補基である。まだ開示された光学フィルムの別の実施形態では、前記有機層は、ＵＶスペクトル範囲の少なくとも１つの部分的な所定波長範囲に電磁放射を吸収する。光学フィルムの別の実施形態では、結合基は、固体層におい
て、主に基板表面の平面内で配向されるフラットな非等軸粒子の非共有結合の化学的結合を介した形成を提供する。開示された光学フィルムの一実施形態では、非共有結合の化学結合は、単水素結合、双極子間相互作用、陽イオン−パイ相互作用、ファンデルワールス相互作用、配位結合、イオン結合、イオン双極子相互作用、多重水素結合、ヘテロ原子を介した相互作用、およびそれらの任意の組み合わせを含むリストから選択される。
光学フィルムの一実施形態では、前記有機層は、水に実質的に溶けない。光学フィルムの別の実施形態では、有機層は、ＵＶスペクトル範囲の少なくとも１つの部分的な所定波長範囲内での電磁放射の吸収を各々保証する構造式（ＩＩＩ）の有機化合物を２種類以上含む。

In the formula, the hydrogen acceptor (A) and the hydrogen donor (D) are independently selected from the list containing NH groups and oxygen (O). In one embodiment of the disclosed optical film, the bonding group includes the heteroatom, COOH, SO ₃ H, H ₂ PO ₃ , NH, NH ₂ , CO, OH, NHR, NR, COOMe, CONH ₂ , CONHNH _2. , SO ₂ NH ₂ , —SO ₂ —NH—SO ₂ —NH ₂ , and any combination thereof, and as described above, the radical R is alkyl or aryl. In another embodiment of the disclosed optical film, at least one binding group is a complementary group. In another embodiment of the optical film still disclosed, the organic layer absorbs electromagnetic radiation in at least one partial predetermined wavelength range of the UV spectral range. In another embodiment of the optical film, the linking group provides for the formation in the solid layer through non-covalent chemical bonding of flat non-equal particles oriented primarily in the plane of the substrate surface. In one embodiment of the disclosed optical film, the non-covalent chemical bond comprises a single hydrogen bond, dipole interaction, cation-pi interaction, van der Waals interaction, coordination bond, ionic bond, ion Selected from a list comprising dipole interactions, multiple hydrogen bonds, interactions through heteroatoms, and any combination thereof.
In one embodiment of the optical film, the organic layer is substantially insoluble in water. In another embodiment of the optical film, the organic layer comprises two or more organic compounds of structural formula (III) each guaranteeing absorption of electromagnetic radiation within at least one partial predetermined wavelength range of the UV spectral range. .

In one embodiment of the disclosed optical film, the heterocyclic molecular system has an axis of symmetry of order k (C _k ) perpendicular to the plane of the heterocyclic molecular system, where k is It is an integer of 3 or more.

  In another embodiment of the disclosed optical film, the heterocyclic molecular system has an expanded non-equal axis configuration with a longitudinal axis. In yet another embodiment of the disclosed optical film, the longitudinal axis of the heterocyclic molecular system has a substantially isotropic alignment in the plane of the substrate.

In yet another embodiment of the disclosed optical film, the longitudinal axis of the heterocyclic molecular system has a substantially anisotropic alignment in the substrate plane.
In one embodiment of the disclosed optical film, the predominantly planar heterocyclic molecular system comprises pyrazine and / or imidazole fragments. Examples of planar bonded heterocycles are shown in Table 1. In another embodiment of the disclosed optical film, the heterocyclic molecular system has the expanded anisoaxial form shown in Table 2. In yet another embodiment of the disclosed optical film, the heterocyclic molecular system is an oligomer comprising an imidazole and / or benzimidazole cycle, and the ring can form hydrogen bonds. Examples of planar bonded heterocycles are shown in Table 3. Here, n is a number in the range of 1-5. In yet another embodiment of the disclosed optical film, a derivative of 1H, 1′H-2,2′-bibenzimidazole, a derivative of 2,2′-bi-1,3-benzoxazole, and 2, Selected from the list comprising derivatives of 2'-bi-1,3-benzoxazole. In another embodiment of the optical film, the organic compound has a structural formula shown in Table 4. In one embodiment of the disclosed optical _{film, -CH 3, -C 2 H 5} , -NO 2, -Cl, -Br, -F, -CF 3, -CN, -NCS, -OH, -OCH 3 And at least one additional substituent selected from a list comprising:, —OC ₂ H ₅ , —OCOCH ₃ , —OCN, —SCN, —NH ₂ , —NHCOCH ₃ , and —CONH ₂ .

  In one embodiment of the optical film, the longitudinal axis of the heterocyclic molecular system has a substantially isotropic alignment in the substrate plane. In another embodiment of the disclosed optical film, the longitudinal axis of the heterocyclic molecular system has a substantially anisotropic alignment in the substrate plane.

In yet another embodiment of the optical film, the solid layer is generally normal to the substrate surface with two refractive indices (nx and ny) corresponding to two mutually perpendicular directions in the plane of the substrate surface. A uniaxial retardation layer possessing one refractive index (nz) in the direction, and these refractive indices are subject to the following conditions: nx = ny> nz In yet another embodiment of the optical film, the solid layer generally corresponds to one refractive index (nz) normal to the substrate surface and two directions perpendicular to each other in the plane of the substrate surface. The biaxial retardation layer possesses two refractive indices (nx and ny), and these refractive indices are subject to the following conditions: nx>ny> nz. In yet another embodiment of the disclosed optical film, the substrate is made of a polymer. In yet another embodiment of the disclosed optical film, the substrate is made of glass. In one embodiment of the disclosed optical film, the back surface of the substrate is covered with an anti-reflective coating or an anti-flashing coating. In one embodiment of the disclosed optical film, the substrate is transparent to electromagnetic radiation in the visible spectral range. In another embodiment, the present invention provides an optical film characterized in that the transmission coefficient of the substrate in the visible spectral range is at least 90%. In yet another embodiment, the optical film further comprises an additional planarizing transparent layer applied on the front surface of the substrate. In another embodiment of the disclosed invention, the optical film includes a reflective layer applied on the back side of the substrate. In one embodiment of the disclosed optical film, the substrate is a specular or diffusive reflector. In yet another embodiment of the disclosed optical film, the substrate is a reflective polarizer. In yet another embodiment, the present invention provides an optical film further comprising an additional transparent adhesive layer applied over the organic layer. In another embodiment of the disclosed invention, the optical film further comprises a protective coating applied over the transparent adhesive layer. In one embodiment of the disclosed invention, the optical film has two or more organic layers, which are electromagnetic radiations within at least one independently selected partial wavelength range of the UV spectral range. Different organic compounds of the structural formula (III) each guaranteeing the absorption of In another embodiment of the disclosed optical film, the solid layer is partially or completely a crystalline layer. In another embodiment of the disclosed invention, the optical film includes two or more organic layers. Here, these layers comprise different organic compounds of the structural formula (III) that compensate for at least one difference in the refractive index (nx, ny or nz) of two adjacent layers.

As disclosed above, the present invention also provides a method of producing an optical film.
In one embodiment of the disclosed method, the predominantly planar heterocyclic molecular system is partially or fully conjugated. Heterocyclic molecular system in another embodiment of the disclosed _{method, -CH 3, -C 2 H 5} , -NO 2, -Cl, -Br, -F, -CF 3, -CN, -NCS, - _{OH, -OCH 3, -OC 2 H} 5, -OCOCH 3, -OCN, -SCN, -NH 2, -NHCOCH 3, and further at least one additional substituent selected from the list comprising -CONH ₂ Including. In yet another embodiment of the disclosed method, the linking group is selected from a list comprising a hydrogen acceptor (A), a hydrogen donor (D), and a group having the structural formula (II).

式中、水素受容体（Ａ）および水素供与体（Ｄ）は、ＮＨ基および酸素（Ｏ）を含むリストから独立して選ばれる。開示された方法の別の実施形態では、前記ヘテロ環式分子系は、窒素、酸素、硫黄、およびそれらの任意の組み合わせを含むリストから選択されるヘテロ原子を含む。

In the formula, the hydrogen acceptor (A) and the hydrogen donor (D) are independently selected from the list containing NH groups and oxygen (O). In another embodiment of the disclosed method, the heterocyclic molecular system comprises a heteroatom selected from the list comprising nitrogen, oxygen, sulfur, and any combination thereof.

According to one embodiment of the disclosed method, at least one of the linking groups is the heteroatom, COOH, SO ₃ H, H ₂ PO ₃ , NH, NH ₂ , CO, OH, NHR, NR, COOMe, _{CONH 2, CONHNH 2, SO 2} NH 2, selected from the list comprising _{-SO 2 -NH-SO 2 -NH 2} , and any combination thereof, the radical R is alkyl or aryl. In one embodiment of the disclosed invention, identical linking groups belonging to different heterocyclic molecular systems form non-covalent chemical bonds between these systems. Such linking groups are called self-bonding or complementary. In one embodiment of the method, the liquid layer ensures the absorption of electromagnetic radiation within a predetermined wavelength subrange at least at one location in the UV spectral range. In another embodiment of the disclosed method, the heterocyclic molecular system has an expanded non-equal axis configuration with a longitudinal axis. An isotropic or anisotropic alignment of the longitudinal axis of the heterocyclic molecular system may be received for the same organic compound. In yet another embodiment of the disclosed method,
Solution concentration, temperature level, humidity, and duration of the drying step may be selected to ensure a nearly isotropic alignment of the longitudinal axis of the heterocyclic molecular system in the substrate plane. In yet another embodiment of the disclosed method, the concentration of the solution, the level of temperature, the humidity, and the duration of the drying step are aligned with a substantially anisotropic alignment of the longitudinal axis of the heterocyclic molecular system in the substrate plane. You may choose to guarantee In one embodiment of the disclosed method, the heterocyclic molecular system has an axis of symmetry C _k perpendicular to the plane of the molecular system, where n is a number greater than or equal to 3. In another embodiment of this method, the predominantly planar heterocyclic molecular system has pyrazine and / or imidazole fragments, and a list of structures comprising structures 1-4 as shown in Table 1 Have an expression. In yet another embodiment of the method, the predominantly planar heterocyclic molecular system has the expanded anisoaxial morphology shown in Table 2. In one embodiment of the disclosed method, the heterocyclic molecular system is an oligomer comprising imidazole and / or benzimidazole cycles, which can form hydrogen bonds. The heterocyclic molecular system may have a structural formula from a list including structures 7-15 shown in Table 3, where n is a number in the range of 1-5. In another embodiment of the still disclosed method, the organic compound is a derivative of 1H, 1′H-2,2′-bibenzimidazole, a derivative of 2,2′-bi-1,3-benzoxazole, And a list comprising derivatives of 2,2′-bi-1,3-benzoxazole. In yet another embodiment of the disclosed method, the organic compound has the structural formula shown in Table 4. In another embodiment of the disclosed method, the non-covalent chemical bond is a single hydrogen bond, a dipole interaction, a cation-pi interaction, a van der Waals interaction, a coordination bond, an ionic bond, an ion Selected from a list comprising dipole interactions, multiple hydrogen bonds, heteroatom interactions, and any combination thereof. In yet another embodiment of the method, the liquid layer further comprises water, a water miscible solvent, an alcohol based solvent, and any combination thereof. In one embodiment of the disclosed method, the preferred solvent is water. In yet another embodiment of the method, the drying is performed in an air stream. In yet another embodiment, the amount of solvent is controlled to provide the liquid layer viscosity necessary to apply the liquid layer by hydrodynamic flow. In yet another embodiment of the disclosed method, the liquid layer viscosity is 2 Pa · s or less. In another embodiment of the invention, the method further includes a pretreatment step prior to application on the substrate. In one embodiment of the disclosed method, the pretreatment includes making the surface of the substrate hydrophilic.
In another embodiment of the disclosed method, the pretreatment includes further application of a planarization layer. In one embodiment of the disclosed invention, the method comprises H ⁺ , Ba ²⁺ , Ca ²⁺ , Mg ²⁺ , Sr ²⁺ , La ³⁺ , Zn ²⁺ , Zr ⁴⁺ , Ce ³⁺ , Y ³⁺ , Yb ³⁺ , Gd ³⁺ , And a post-treatment step with a solution of any water-soluble inorganic salt having a cation selected from the list comprising any combination thereof. In one embodiment of the disclosed method, the applying step and the post-processing step occur simultaneously. In another embodiment of the disclosed method, the drying step and the post-processing step occur simultaneously. In another embodiment of the method still disclosed, the post-treatment step is performed after drying. In yet another embodiment of the disclosed method, the application is performed using an isotropic solution. In yet another embodiment of the disclosed method, the application is performed using a lyotropic liquid crystal solution. In one embodiment of the disclosed method, the liquid layer is made from a gel. In one embodiment of the disclosed method, the application is performed using a viscous liquid phase. In yet another embodiment of the disclosed invention, the post-application method further includes an alignment operation applied on the liquid layer on the substrate. In one embodiment of the disclosed method, the sequence of precipitation and drying technical operations is repeated two or more times to form each resulting solid phase using a liquid layer. This liquid layer is made of the same or different organic compound as used in the previous cycle and absorbs electromagnetic radiation within at least one wavelength subrange independently selected from the UV spectral range. Have In one embodiment of the disclosed invention, the method includes applying an application operation applied to the liquid layer on the substrate after or simultaneously with an application step different from that used in the previous cycle. At least one of the refractive indexes (nx, ny, or nz) is different between the two layers.

  As disclosed above, the present invention further provides 2,2'-bibenzheteroazole heterocyclic compounds. In one embodiment of the invention, the 2,2'-bibenzheteroazole heterocyclic compound has a structural formula from the list comprising structures 16-34 shown in Table 4.

  Objects and advantages of the present invention will become apparent upon reading the detailed description of the examples provided below and the appended claims, and upon reference to the drawings.

The conceptual diagram which shows the example in the general case where the principal axes (A, B, C) of the dielectric constant tensor are arbitrarily oriented with respect to the xyz frame. The conceptual diagram which shows the orientation of the principal axis of a specific dielectric constant tensor with respect to the natural coordinate frame of a positive C plate. The conceptual diagram which shows orientation of the principal axis of a specific dielectric constant tensor regarding the natural coordinate frame of a negative C plate. The perspective view which shows the definition of a viewing angle direction. Model schematically showing an organic compound including a hydrophilic and discotic heterocyclic molecular system (Het) having three linking groups. Model schematically showing an organic compound comprising a flat heterocyclic molecular system having an axis of symmetry C _3. Model schematically illustrating an organic compound comprising a flat heterocyclic molecular system exhibiting an expanded non-equal axis form with a longitudinal axis. Model showing one structure of flat anisoaxial particles formed by the heterocyclic molecular system shown in Table 1 as Structure 1. Model showing another structure of flat non-equal axis particles formed by the heterocyclic molecular system shown in Table 1 as Structure 1. FIG. 6 is a model schematically showing one possible structure of flat non-axial axes formed by an organic compound having the structural formula shown in FIG. FIG. 7 is a model illustrating another possible structure of flat non-equal axes particles formed by an organic compound having the structural formula shown in FIG. FIG. 7 is a further model that schematically illustrates another possible structure of flat non-equal axes particles formed by an organic compound having the structural formula shown in FIG. Model showing the structure of flat non-equal axis particles formed by the heterocyclic molecular system shown in Table 2 as Structure 5. The refractive index spectrum of the optical film by this invention. NMR ¹ H spectrum (Bruker Avance 300 instrument, d ₆ -dimethyl sulfoxide). Sectional drawing of the optical film on a board | substrate shown with an additional adhesion layer and a protective layer. Sectional drawing of the optical film which has an additional antireflection layer. Sectional drawing of the optical film which has an additional reflection layer. Sectional drawing of the optical film which has a diffusion or specular reflector as a board | substrate.

FIG. 4 illustrates one embodiment of an organic compound comprising a generally flat disc-shaped heterocyclic molecular system and at least three linking groups. A heterocyclic molecular system having the structural formula 1 shown in Table 1 can be used as such a disk-shaped heterocyclic molecular system. The position of the linking group is indicated by oxygen ion (O ⁻ ).
The heterocyclic molecular system has a third axis of symmetry that is oriented perpendicular to its plane. Certain heterocyclic molecular systems contain a nitrogen cation (N ⁺ ) that acts as a heteroatom. As a result, electric dipoles (O ⁻ —N ⁺ ) are formed in the plane of the heterocyclic molecular system, which renders the system hydrophilic. In the process of preparing an organic compound solution, the heterocyclic molecular system and the linking group form flat non-equal particles (dynamic particles) by non-covalent chemical bonds between adjacent heterocyclic molecular system linking groups. To do. During application of the reaction mixture onto the substrate, certain portions of these flat non-equal particles are destroyed due to the breakage of weak non-covalent bonds. This disruption reduces the viscosity of the reaction mixture and promotes its orientation by hydrodynamic flow. The planes of the non-equiaxial particles are oriented parallel to the substrate plane due to the hydrophilic nature of the heterocyclic molecular system, producing their effective homeotropic orientation. Thereafter, the broken non-covalent chemical bonds within the non-equal axis particles are restored.

FIG. 5 schematically illustrates one embodiment of an organic compound comprising a flat heterocyclic molecular system, which system is a symmetrical C ₃ axis oriented perpendicular to the plane of the heterocyclic molecular system. Have Heterocyclic molecular systems contain two types of linking groups. The linking groups shown as A ₁ , A ₂ , and A ₃ can form hydrogen bonds (H bonds) and can function as hydrogen acceptors. Other linking groups (D ₁ H, D ₂ H, and D ₃ H) can further form hydrogen bonds (H bonds) and act as hydrogen donors. In the process of preparing a solution of an organic compound, the heterocyclic molecular system and the linking group form flat non-axial axes particles (dynamic particles) due to H bonds between the linking groups of adjacent heterocyclic molecular systems.

FIG. 6 schematically illustrates one embodiment of an organic compound comprising a flat heterocyclic molecular system that exhibits an expanded anisoaxial form with a longitudinal axis (aa). Heterocyclic molecular systems contain two types of linking groups. The linking groups shown as A ₁ , A ₂ , A ₃ , and A ₄ can form hydrogen bonds (H bonds) and act as hydrogen acceptors. Other linking groups (D ₁ H, D ₂ H, D ₃ H, and D ₄ H) are also capable of forming hydrogen bonds (H bonds) and act as hydrogen donors. In the process of preparing a solution of an organic compound, the heterocyclic molecular system and the linking group form flat non-axial axes particles (dynamic particles) due to H bonds between the linking groups of adjacent heterocyclic molecular systems.

Figures 7a and 7b schematically show some possible structures of flat non-equal particles (polymer particles). In this embodiment of the disclosed invention, non-covalent bonds, one heterocyclic molecular systems cations (N ⁺⁾ and the adjacent heterocyclic molecular system anion (O ^-) between, it is formed (See FIG. 7a). When the linking group is represented by a carboxy group, an H bond is formed between the hydroxyl group OH of one carboxy group and the oxygen ion of another group (see FIG. 7b). The size of the non-equal axis particles is preferably 1 micron or less.

FIG. 8 schematically shows one possible structure of flat non-equal axis particles (polymer particles) formed by an organic compound having the structural formula shown in FIG. In this embodiment of the disclosed invention, flat non-equal particles are formed by following H bonds. That is, A ₁ -HD ₃ , A ₂ -HD ₁ , and A ₃ -HD ₂ . FIG. 9 schematically shows another possible structure of flat non-equal axis particles (polymer particles) formed by an organic compound having the structural formula shown in FIG. A characteristic of these flat non-equal axes particles is that they are oriented approximately perpendicular to the longitudinal axis of the adjacent planar heterocyclic molecular system. FIG. 10 schematically shows yet another possible structure of flat non-equal axis particles (polymer particles) formed by an organic compound having the structural formula shown in FIG. These flat non-equal axis particles are characterized by a substantially parallel orientation of the longitudinal axes of adjacent planar heterocyclic molecular systems. In this embodiment of the disclosed invention, flat non-equal particles are formed by following H bonds. That is, A ₁ -HD ₂ , A ₂ -HD ₁ , A ₃ -HD ₄ , and A ₄ -HD ₃ .

In another embodiment of the present invention, the optical film is based on an organic compound comprising a heterocyclic molecular system shown in Table 2 as Structure 5, which structure exhibits an elongated ribbon-like configuration and is hydrophilic. And has two terminal carboxyl groups as linking groups. In organic compound solutions, such molecular systems form equiaxed particles having the configuration shown in FIG.
When a solution of organic compound is applied on a substrate, for example by extrusion, the equiaxed particles and thus the linking groups are oriented along the coating direction (Ox). FIG. 7 schematically shows an embodiment, in which equiaxed particles consist of straight chains having linking groups capable of forming H-bonds. Since heterocyclic molecular systems are hydrophilic, their planes are oriented parallel to the substrate (xOy plane). The optical film according to this embodiment is anisotropic and its refractive index is substantially different along the three axes. That is, nx>ny> nz.

In order that the present invention may be more readily understood, reference is made to the following examples, which are intended to illustrate the invention and are not intended to limit its scope.
Example 1
The first example is tricarboxy-5,11,17-trimethylbis [3,1] benzimidazo [1 ′, 2 ′: 3,4]; 1 ″, 2 ″: 5,6] [1,3 , 5] The synthesis of a mixture of triazino [1,2-a] [3,1] benzimidazole-5,11,17-triium bromide is described.

Ａ． １Ｈ−ベンゾイミダゾール−６−カルボキシル酸の合成
３、４−ジアミノベンゾイン酸（２０ｇ、０．１３ｍｏｌ）を、冷やしながらギ酸（１２０ｍｌ）に懸濁した。その後、塩酸（１２ｍｌ）を加えた。得られた反応生成物を室温で２４時間アジテートした。反応混合物をガラス繊維フィルターでろ過した。その後、ろ過ケークを水（４００ｍｌ）に溶かした。ｐＨをアンモニア溶液で２．０に調節して反応生成物を一晩アジテートした。得られた懸濁液をろ過した。濾液のｐＨをアンモニア溶液で３．０に調節した。また、反応生成物を２時間アジテートした。沈殿物をろ過し、〜１００°Ｃで乾燥させた。Ｈ^１ＮＭＲ（ブルカーアバンス（Ｂｒｕｃｋｅｒ Ａｖａｎｃｅ）−３００、ＤＭＳＯ−ｄ_６、δ、ｐｐｍ）：７．６９５（ｄ、Ｈ、ＣＨ^Ａｒ（７））；７．８７７（ｄｄ、Ｈ、ＣＨ^Ａｒ（６））；８．２５（ｄ、Ｈ、ＣＨ^Ａｒ（４））；８．４４（ｓ、Ｈ、（ｓ，Ｈ、ＣＨ^Ａｒ（２））；１２．８２（ｓ，２Ｈ、ＮＨ、ＣＯＯＨ）。収量１１．３ｇ（５４％）．
Ｂ． ２−ブロモ−１−メチル−１Ｈ−ベンゾイミダゾール−５（６）−カルボン酸の合成
メタノール（２００ｍｌ）中に臭素（６４ｍｌ、１．２５ｍｏｌ）を含む溶液を、メタノール（２７０ｍｌ）中に１Ｈベンズイミダゾール−６−カルボン酸（２０ｇ、０．１２ｍｏｌ）を含む懸濁液に、冷やしながら投入した。反応生成物を室温で３日間アジテートした。その溶液体積をロータリー・エバポレータ上で１２０ｍｌまで減少させた後、得られた濃縮物をアセトン（１．７ｌ）に加えて一晩アジテートした。沈殿物をろ過し、アセトンで濯ぎ、さらに乾燥させた。Ｈ^１ＮＭＲ（ブルカーアバンス（Ｂｒｕｃｋｅｒ Ａｖａｎｃｅ）−３００、ＤＭＳＯ−ｄ_６、δ、ｐｐｍ）：３．９４（ｓ、３Ｈ、ＣＨ_３）；
７．９９５（ｄ、Ｈ、ＣＨ^Ａｒ（７））；８．１４（ｄｄ、Ｈ、ＣＨ^Ａｒ（６））；８．３９（ｄ、Ｈ、ＣＨ^Ａｒ（４））；９．７９（ｓ、Ｈ、ＣＯＯＨ）。収量２０．５ｇ（６５％）。
Ｃ． ５，１１，１７−トリメチルビス［３，１］ベンズイミドアゾ［１’，２’：３，４；１”，２”：５，６］［１，３，５］トリアジノ［１，２−ａ］ベンズイミダゾール−５，１１，１７−トリイウム臭化物の合成
２−ブロモ−１−メチル−１Ｈ−ベンズイミダゾール−５（６）−カルボン酸（２０ｇ、０．０８ｍｏｌ）をＮ−メチルピロリドン（１００ｍｌ）に投入した。反応生成物を１５０〜１５５℃で６時間アジテートした。自己冷却の後、それをクロロホルム（２ｌ）に添加し、２時間撹拌した。沈殿物をろ過した。ろ過ケークをろ過し、クロロホルム（７００ｍｌ）に懸濁し、ろ過し、さらにクロロホルムで濯いだ。生成物を〜９０℃で乾燥した。Ｈ^１ＮＭＲ（ブルカーアバンス（Ｂｒｕｃｋｅｒ Ａｖａｎｃｅ）−３００、ＤＭＳＯ−ｄ_６、δ、ｐｐｍ）：４．１２（ｓ、３Ｈ、ＣＨ_３）；４．１４（ｓ、３Ｈ、ＣＨ_３）；４．１６（ｓ、３Ｈ、ＣＨ_３）；４．１８；（Ｓ、３Ｈ、ＣＨ_３）；８．１０５（ｍ、６Ｈ、３^＊ＣＨ^ＡｒＣＨ^Ａｒ）；８．４８５；（ｍ、３Ｈ、３^＊ＣＨ^Ａｒ）；９．９０（ｓ、Ｈ、ＣＯＯＨ^Ａｒ）；９．７０５（ｍ、３Ｈ、ＣＯＯＨ）。生成物を〜９０℃で乾燥した。収量１８．８ｇ（９０％）。
実施例２
第二の実施例では、ビスベンズイミダゾ［１’，２’：３，４；１”，２”：５，６］［１，３，５］トリアジノ［１，２−ａ］ベンズイミダゾール−トリスルホン酸の混合物の合成を説明する。

A. Synthesis of 1H-benzimidazole-6-carboxylic acid 3,4-Diaminobenzoic acid (20 g, 0.13 mol) was suspended in formic acid (120 ml) while cooling. Then hydrochloric acid (12 ml) was added. The resulting reaction product was agitated for 24 hours at room temperature. The reaction mixture was filtered through a glass fiber filter. Thereafter, the filter cake was dissolved in water (400 ml). The reaction product was agitated overnight with pH adjusted to 2.0 with ammonia solution. The resulting suspension was filtered. The pH of the filtrate was adjusted to 3.0 with ammonia solution. The reaction product was agitated for 2 hours. The precipitate was filtered and dried at ~ 100 ° C. H ¹ NMR (Brucker Avance-300, DMSO-d ₆ , δ, ppm): 7.695 (d, H, CH ^Ar (7)); 7.877 (dd, H, CH ^Ar (6 8.25 (d, H, CH ^Ar (4)); 8.44 (s, H, (s, H, CH ^Ar (2)); 12.82 (s, 2H, NH, COOH) Yield 11.3 g (54%).
B. Synthesis of 2-Bromo-1-methyl-1H-benzimidazole-5 (6) -carboxylic acid A solution of bromine (64 ml, 1.25 mol) in methanol (200 ml) was dissolved in 1H benzimidazole in methanol (270 ml). The suspension containing -6-carboxylic acid (20 g, 0.12 mol) was added while cooling. The reaction product was agitated at room temperature for 3 days. The solution volume was reduced to 120 ml on a rotary evaporator and the resulting concentrate was added to acetone (1.7 l) and agitated overnight. The precipitate was filtered, rinsed with acetone and further dried. H ¹ NMR (Brucker Avance-300, DMSO-d ₆ , δ, ppm): 3.94 (s, 3H, CH ₃ );
7.995 (d, H, CH ^Ar (7)); 8.14 (dd, H, CH ^Ar (6)); 8.39 (d, H, CH ^Ar (4)); 9.79 (s , H, COOH). Yield 20.5 g (65%).
C. 5,11,17-trimethylbis [3,1] benzimidoazo [1 ′, 2 ′: 3,4; 1 ″, 2 ″: 5,6] [1,3,5] triazino [1,2-a] Synthesis of benzimidazole-5,11,17-triium bromide 2-Bromo-1-methyl-1H-benzimidazole-5 (6) -carboxylic acid (20 g, 0.08 mol) was added to N-methylpyrrolidone (100 ml). did. The reaction product was agitated at 150-155 ° C. for 6 hours. After self-cooling, it was added to chloroform (2 l) and stirred for 2 hours. The precipitate was filtered. The filter cake was filtered, suspended in chloroform (700 ml), filtered, and further rinsed with chloroform. The product was dried at ~ 90 ° C. H ¹ NMR (Brucker Avance-300, DMSO-d ₆ , δ, ppm): 4.12 (s, 3H, CH ₃ ); 4.14 (s, 3H, CH ₃ ); 4.16 (S, 3H, CH ₃ ); 4.18; (S, 3H, CH ₃ ); 8.105 (m, 6H, 3 ^* CH ^Ar CH CH ^Ar ); 8.485; (m, 3H, 3 ^* CH ^Ar ); 9.90 (s, H, COOH ^Ar ); 9.705 (m, 3H, COOH). The product was dried at ˜90 ° C. Yield 18.8 g (90%).
Example 2
In a second example, bisbenzimidazo [1 ′, 2 ′: 3,4]; 1 ″, 2 ″: 5,6] [1,3,5] triazino [1,2-a] benzimidazole-tri The synthesis of a mixture of sulfonic acids is described.

Ａ．ビスベンズイミダゾ［１’，２’：３，４；１”，２”：５，６］［１，３，５］トリアジノ［１，２−ａ］ベンズイミダゾールの合成
２−クロロ−１Ｈベンゾイミダゾール（４ｇ、０．０２６ｍｏｌ）を２００〜２２０℃まで加熱し、３０分アジテートした（塩化水素の発生が停止するまで）。ニトロベンゼンを反応生成物へ添加し、アジテートしながら２５分間にわたり沸騰させた。〜８０℃に自冷させた後、それをろ過し、アセトンで濯いだ。ろ過ケークを〜１００℃で乾燥させた。収量２．１ｇ（７０％）。
Ｂ． ビスベンズイミダゾ［１’，２’：３，４；１”，２”：５，６］［１，３，５］トリアジノ［１，２−ａ］ベンズイミダゾール−トリスルホン酸の混合物の合成
ビスベンズイミダゾ［１’，２’：３，４；１”，２”：５，６］［１，３，５］トリアジノ［１，２−ａ］ベンズイミダゾール（２．０ｇ、０．００６ｍｏｌ）を２０％発煙硫酸（２０ｍｌ）に投入して一晩アジテートした。その反応生成物を水（２８．２ｍｌ）で希釈した後、沈殿物をろ過し、濃塩酸、１，４−ジオキサン、およびアセトンで濯いだ。生成物をデシケーター内で乾燥させた。収量１．３２ｇ（４０％）。
実施例３（Ａ０５６）
次の実施例では、ヘテロ環式化合物の溶液からの光学フィルムの調製について説明する
。

A. Synthesis of bisbenzimidazo [1 ′, 2 ′: 3,4; 1 ″, 2 ″: 5,6] [1,3,5] triazino [1,2-a] benzimidazole 2-Chloro-1H benzimidazole (4 g, 0.026 mol) was heated to 200-220 ° C. and agitated for 30 minutes (until hydrogen chloride evolution ceased). Nitrobenzene was added to the reaction product and boiled for 25 minutes with agitation. After being allowed to cool to ˜80 ° C., it was filtered and rinsed with acetone. The filter cake was dried at ~ 100 ° C. Yield 2.1 g (70%).
B. Synthesis of bisbenzimidazo [1 ′, 2 ′: 3,4; 1 ″, 2 ″: 5,6] [1,3,5] triazino [1,2-a] benzimidazole-trisulfonic acid mixture Benzimidazo [1 ′, 2 ′: 3,4; 1 ″, 2 ″: 5,6] [1,3,5] triazino [1,2-a] benzimidazole (2.0 g, 0.006 mol) Agitated overnight in 20% fuming sulfuric acid (20 ml). After the reaction product was diluted with water (28.2 ml), the precipitate was filtered and rinsed with concentrated hydrochloric acid, 1,4-dioxane, and acetone. The product was dried in a desiccator. Yield 1.32 g (40%).
Example 3 (A056)
The following examples describe the preparation of optical films from solutions of heterocyclic compounds.

Tricarboxy-5,11,17-trimethylbis [3,1] benzimidazo [1 ′, 2 ′: 3, 4; 1 ″, 2 ″: 5, 6] [1, 3,] obtained in Example 1 5] 7.5 g of a mixture of triazino [1,2-a] [3,1] benzimidazole-5,11,17-triium bromide is dissolved in 42.5 g of deionized water, and the entire solid phase is decomposed. At 20 ° C. until 21.3 g of 5% ZnCl ₂ solution and 28.7 g of deionized water were added and the mixture was stirred under ambient conditions for 1 hour.

  To prepare a soda lime LCD quality glass slide for coating, it was treated in 10% NaOH solution for 30 minutes, rinsed with deionized water, and dried in a stream of air with the aid of a compressor. Prior to coating, the sample was rinsed with isopropyl alcohol. The resulting solution was applied on a glass plate with a Mayer rod # 2.5 at a temperature of 20 ° C. and a relative humidity of 65%. The film was dried at the same humidity and temperature in a gentle stream of air.

The refractive index spectrum of the obtained film is shown in FIG. The resulting film is optically isotropic in the plane and exhibits a high delay in the vertical direction.
Example 4
This example illustrates the synthesis of a 2,2′-bibenzheteroazole heterocyclic compound represented by Structural Formula (IV).

1H, 1′H-2,2′-bibenzimidazole-5,5′-dicarboxylic acid (1)
To a suspension of 3,4-diaminobenzoic acid (1.0 g, 6.6 nmol) in anhydrous methanol (100 ml), O-methyl-1,1,1-trichloroacetimidate was added (0 .4 mL, 0.57 g, 3.2 mmol). The reaction mixture was stirred for 48 hours under ambient conditions. The resulting yellow solid was filtered off and dried in vacuo until constant weight. Yield 0.43 g (41%). For further purification, 1H, 1′H-2,2′-bibenzimidazole-5,5′-dicarboxylic acid was dissolved in dimethyl sulfoxide at a ratio of 0.85 g / 37 mL, and the resulting solution was dissolved in Water was added slowly (5 mL). The mixture was stirred for 30 minutes. The resulting solid was filtered off, washed with ethanol (2 × 30 mL) and dried in vacuo until constant weight. NMR ¹ H spectrum (Brucker Avance 600 instrument, solvent d ₆ -dimethyl sulfoxide; δ, ppm; J, Hz): 7.74 d. _{^{d (2H b, 3 J ba}} = 7.5), 7.93d (2H a, 3 J ab = 7.5), 8.28d (2H X). 12.89 br. s (2NH and 2COOH) (13.94br.s (2NH and 2COOH)). Mass spectrum (MALDI positive mode (Ultraflex TOF / TOF
Bruker Daltonics Inc. (Bruker Daltonics) ^{instrument): 322 (100%) [} M + ·], 304 (45%) [M + · -H 2 O], 277 (50%) [M + · -CO 2 H].

Dimethyl 1H, 1′H-2,2′-bibenzimidazole-5,5′-dicarboxylate (2)
Methyl 3,4-diaminobenzoate (3.3 g, 19.9 mmol) was dissolved in anhydrous MeOH (100 mL). To the resulting solution, O-methyl-1,1,1-trichloroacetimidate (1.75 g, 1.25 mL, 9.9 mmol) was added. The reaction mixture was stirred for 48 h under ambient conditions. The formed precipitate was filtered off with methanol (2 × 20 mL) and dried in vacuo until constant weight. Yield 1.0 g (28%).

1H, 1′H-2,2′-bibenzimidazole-5,5′-disulfonic acid (4)
In a three-necked flask, 3,4-diaminobenzenesulfonic acid (8.0 g, 42.5 mmo
l) and anhydrous MeOH (0.85 L) were charged. O-methyl-1,1,1-trichloroacetimidate was added (2.8 mL, 3.74 g, 21.2 mmol). The resulting suspension was stirred for 24 hours under ambient conditions. After this time, an additional amount of 0-methyl-1,1,1-trichloroacetimidate was added (1.4 mL, 1.87 g, 10.5 mmol) and the reaction mixture was then stirred for 72 hours under ambient conditions. The mixture was heated at 50 ° C. for 3 hours and more triethylamine (14 mL, 9.4 g, 93.5 mmol) was added. Stirring was continued at this temperature for 18 hours. The reaction mixture was then cooled to 30 ° C. and a concentrated stream of dry HCl was passed through the solution until a precipitate formed. The suspension was filtered off at 40 ° C. and the precipitate was washed with MeOH (4 × 150 mL, each time the suspension was stirred for 10-15 minutes) and MeOH-HCl 3.5% solution (100 ml, stirred for 1 hour). It was. The product 1H, 1′H-2,2′-bibenzimidazole-5,5′-disulfonic acid was yellowish white or colorless and weighed 3.5 g, yield 42%. It may contain its own hydrochloride as a salt. NMR ¹ H spectrum (Brucker Avance 300 instrument, solvent d ₆ -dimethyl sulfoxide; δ, ppm; J, Hz): 5.27 br. s (—SO ₃ H instead of H ₂ O and NH) 7.73 ^m (2H ^a , 2H ^b ), 8.01 br. s (2H ^x ), NMR ¹³ C { ¹ H} spectrum (Brucker Avance 300 instrument, solvent d ₆ -dimethyl sulfoxide; δ, ppm): 113.00, 115.41, 123.27, 136. 44, 137.60, 142.24, 145.34.

1H, 1'H-2,2'-bibenzimidazole-5-sulfonic acid (3a) via direct sulfonation reaction, 1H, 1'H-2,2'-bibenzimidazole-4-sulfonic acid ( 3b) Mixture of 1H, 1′H-2,2′-bibenzimidazole-5,5′-disulfonic acid (4) Insert bibenzimidazole (0.50 g, 2.1 mmol) into 20% fuming sulfuric acid. did. The resulting solution was stirred at 30 ° C. for 2 hours, then poured onto ice (5 g), the separated white precipitate was removed by centrifugation and immediately added with a 36% aqueous solution of hydrogen chloride (5 mL). A solution was formed. Concentrate the solution to half the initial volume, dilute with water (5 mL), cool the resulting heterogeneous mixture to + 10 ° C., filter out the precipitate, centrifuge to remove water (5 mL) The obtained colorless solid was dried in vacuum to obtain a yield of 0.07 g. The mixture is soluble in 10% HCl. NMR ¹ H spectrum (Brucker Avance 300 instrument, d ₆ -dimethyl sulfoxide), see FIG.
Example 5
This example illustrates the preparation of an optical film from an aqueous solution of 1H, 1′H-2,2′-bibenzimidazole-5,5′-dicarboxylic acid in the presence of triethylamine. 1H, 1′H-2,2′-bibenzimidazole-5,5′-dicarboxylic acid is synthesized as described in Example 4. Hand coating was performed using a rod 1.5HS. A thick film (1-3 μm) was obtained using a 20-25% solution. Such a thickness can be obtained from a more viscous solution. FIG. 11 schematically shows a possible structure of flat non-equal particles (polymer particles). In this example of the disclosed invention, two types of H bonds were formed. 1) between a cation (N ⁺ ) of one heterocyclic molecular system and an anion (O ⁻ ) of an adjacent heterocyclic molecular system, and 2) oxygen of an adjacent heterocyclic molecular system. Formed between two atoms.
Example 6
Explains the synthesis of a mixture of bisbenzimidazo [1 ', 2': 3,4; 1 ", 2": 5,6] [1,3,5] triazino [1,2-a] benzimidazole-tricarboxylic acid To do.

Ｄ．メチル２−オキソ−２，３−ジヒドロ−１Ｈ−ベンズイミダゾール−６−カルボン酸塩の合成
メチル３，４−ジアミノベンゾエート二塩酸塩（２０ｇ、０．０８ｍｏｌ）を尿素（６．５４ｇ、０．１１ｍｏｌ）と混合した。反応混合物を〜１５０℃で７時間加熱した。冷やした後に粉体を水（４００ｍｌ）に懸濁し、最後のものｐＨを塩酸で０．４５に合わせた。沈殿物をろ過し、さらに水および塩酸（ｐＨ＝１．５）で濯いだ。得られたろ過ケークを〜１００℃で乾燥させた。収量１５．７ｇ（９７％）。
Ｅ．メチル２−クロロ−１Ｈ−ベンズイミダゾール−６−カルボン酸塩の合成
メチル２−オキソ−２，３−ジヒドロ−１Ｈ−ベンズイミダゾール−６−カルボン酸塩（４３ｇ、０．２２ｍｏｌ）をオキシ塩化リン（２８６ｍｌ）に投入した。沸騰反応生成物を介して乾燥塩化水素を１２時間泡立てた。冷やした後、反応生成物を氷および水（２ｋｇ）の混合物に注いだ。沈殿物をろ過して取り出した。ろ過物を水（１．２５ｌ）およびアンモニア溶液（〜８００ｍｌ）で希釈した。その後、ｐＨをアンモニア溶液で５．６に合わせた。沈殿物をろ過し、水で濯いだ。収量３９．５ｇ（８４％）。
Ｆ．トリメチルビスベンズイミダゾ［１’，２’：３，４；１”,２”：５，６］［１，
３，５］トリアジノ［１，２−ａ］ベンズイミダゾール−トリカルボン酸塩の合成
メチル２−クロロ−１Ｈ−ベンズミダゾール−６−カルボン酸塩（３８ｇ、０．１８ｍｏｌ）を１８５〜１９０℃で１０時間加熱した。収量３０．３ｇ（９６％）。
Ｇ．ビスベンズイミダゾ［１’，２’：３，４；１”,２”：５，６］［１，３，５］ト
リアジノ［１，２−ａ］ベンズイミダゾールトリカルボン酸の合成
トリメチルビスベンズイミダゾ［１’，２’：３，４；１”,２”：５，６］［１，３
，５］トリアジノ［１，２−ａ］ベンズイミダゾール−トリカルボン酸塩（３０ｇ、０．０６ｍｏｌ）を水酸化カリウムの５％溶液（２５０ｍｌ）に投入し、１．５時間沸騰させた。冷やした後、得られた溶液をろ過し、塩化水素溶液で中性にした。次に、溶液のｐＨを塩酸で１．２５に合わせた。沈殿物をろ過し、水で濯ぎ、〜１００℃で乾燥させた。質量スペクトル（ウルトラフレックス（Ｕｉｔｒａｆｌｅｘ）ＴＯＦ／ＴＯＦ（ブルカー・ダルトニクス社（Ｂｒｕｋｅｒ Ｄａｌｔｏｎｉｃｓ）ドイツ ブレーメン（Ｂｒｅｍｅｎ， Ｇｅｒｍａｎｙ）所在））：Ｍ／Ｚ＝４８０（ＦＷ＝４８０．３９）。収量２６．３ｇ（９５％）
実施例７
図１４は、基板１上で形成された光学フィルムの断面図を示す。フィルムは有機質層２、粘着剤層３、および保護材４を含む。
実施例８
上記の光学フィルムを、基板上に形成された追加反射防止層５を有するＬＣＤ前面に適用する（図１５）。例えば、二酸化ケイ素ＳｉＯ_２の反射防止層は、ＬＣＤ前面から反射された光の一部を３０％減少させた。
実施例９
電気光学装置またはＬＣＤ前面に上記の光学フィルムを適用したまま、追加反射層６を
基板上に形成することができる（図１６）。反射層は、例えば、アルミニウム膜を堆積させることによって得ることも可能である。
実施例１０
光学フィルム２は、基板（図１７）としての機能を果たす拡散または鏡面反射体６に適用される。反射体層６を平坦化層７（オプション）で覆うことも可能である。
平坦化層は、ポリウレタン、アクリルポリマー、あるいは他の平坦化材料で作製してもよい。有機層を、実施例３に記述された方法を用いて作る。粘着剤層３および保護材４を光学フィルム上に適用する。
実施例１１
この実施例では、反射体層６は半透明である。有機質層２は、基板（図１７）としての機能を果たす拡散または鏡面反射体６の上に適用される。反射体層６を平坦化層７（オプション）で覆うことも可能である。ポリウレタンまたはアクリルポリマーまたは他の材料を用いて、この平坦化層を作製してもよい。

D. Synthesis of methyl 2-oxo-2,3-dihydro-1H-benzimidazole-6-carboxylate Methyl 3,4-diaminobenzoate dihydrochloride (20 g, 0.08 mol) was urea (6.54 g, 0.11 mol) ). The reaction mixture was heated at ˜150 ° C. for 7 hours. After cooling, the powder was suspended in water (400 ml) and the final pH was adjusted to 0.45 with hydrochloric acid. The precipitate was filtered and further rinsed with water and hydrochloric acid (pH = 1.5). The resulting filter cake was dried at ~ 100 ° C. Yield 15.7 g (97%).
E. Synthesis of methyl 2-chloro-1H-benzimidazole-6-carboxylate Methyl 2-oxo-2,3-dihydro-1H-benzimidazole-6-carboxylate (43 g, 0.22 mol) was added to phosphorus oxychloride ( 286 ml). Dry hydrogen chloride was bubbled through the boiling reaction product for 12 hours. After cooling, the reaction product was poured into a mixture of ice and water (2 kg). The precipitate was filtered out. The filtrate was diluted with water (1.25 l) and ammonia solution (˜800 ml). The pH was then adjusted to 5.6 with ammonia solution. The precipitate was filtered and rinsed with water. Yield 39.5 g (84%).
F. Trimethylbisbenzimidazo [1 ′, 2 ′: 3, 4; 1 ″, 2 ″: 5, 6] [1,
Synthesis of 3,5] triazino [1,2-a] benzimidazole-tricarboxylate Methyl 2-chloro-1H-benzmidazole-6-carboxylate (38 g, 0.18 mol) heated at 185-190 ° C. for 10 hours did. Yield 30.3 g (96%).
G. Synthesis of bisbenzimidazo [1 ′, 2 ′: 3,4; 1 ″, 2 ″: 5,6] [1,3,5] triazino [1,2-a] benzimidazoletricarboxylic acid Trimethylbisbenzimidazo [ 1 ', 2': 3, 4; 1 ", 2": 5, 6] [1, 3
, 5] triazino [1,2-a] benzimidazole-tricarboxylate (30 g, 0.06 mol) was charged into a 5% solution of potassium hydroxide (250 ml) and boiled for 1.5 hours. After cooling, the resulting solution was filtered and neutralized with a hydrogen chloride solution. The pH of the solution was then adjusted to 1.25 with hydrochloric acid. The precipitate was filtered, rinsed with water and dried at ~ 100 ° C. Mass spectrum (Ultraflex TOF / TOF (Bruker Daltonics, Bremen, Germany)): M / Z = 480 (FW = 480.39). Yield 26.3 g (95%)
Example 7
FIG. 14 shows a cross-sectional view of the optical film formed on the substrate 1. The film includes an organic layer 2, an adhesive layer 3, and a protective material 4.
Example 8
The above optical film is applied to the front surface of the LCD having the additional antireflection layer 5 formed on the substrate (FIG. 15). For example, a silicon dioxide SiO ₂ antireflective layer reduced some of the light reflected from the LCD front by 30%.
Example 9
The additional reflective layer 6 can be formed on the substrate while the optical film is applied to the electro-optical device or the LCD front surface (FIG. 16). The reflective layer can also be obtained, for example, by depositing an aluminum film.
Example 10
The optical film 2 is applied to a diffusing or specular reflector 6 that functions as a substrate (FIG. 17). It is also possible to cover the reflector layer 6 with a planarizing layer 7 (optional).
The planarization layer may be made of polyurethane, acrylic polymer, or other planarization material. The organic layer is made using the method described in Example 3. The pressure-sensitive adhesive layer 3 and the protective material 4 are applied on the optical film.
Example 11
In this embodiment, the reflector layer 6 is translucent. The organic layer 2 is applied on a diffusing or specular reflector 6 that serves as a substrate (FIG. 17). It is also possible to cover the reflector layer 6 with a planarizing layer 7 (optional). This planarization layer may be made using polyurethane or acrylic polymers or other materials.

Claims (97)

An organic compound of structural formula (I) comprising:

Where Het is a predominantly planar heterocyclic molecular system having hydrophilicity,
B is a linking group,
p is 3, 4, 5, 6, 7, or 8,
S is a group that gives the solubility of the organic compound,
m is 0, 1, 2, 3, 4, 5, 6, 7 or 8;
The organic compound is transparent to electromagnetic radiation in the visible spectral range of 400-700 nm, and the solution of the compound or its salt is such that the plane of the heterocyclic molecular system is mainly parallel to the plane of the substrate An organic compound capable of forming a substantially transparent optical layer on a substrate so that it is oriented. The organic compound according to claim 1, wherein the linking group B results in the formation of tabular grains from biomolecules in solution by non-covalent chemical bonding. The organic compound according to claim 2, wherein at least one linking group B provides an unstable equilibrium of tabular grains by the solution. The non-covalent chemical bonds include single hydrogen bonds, dipole interactions, cation-pi interactions, van der Waals interactions, coordination bonds, ionic bonds, ionic dipole interactions, multiple hydrogen bonds, heterogeneous bonds. The organic compound according to claim 2 or 3, selected from the group consisting of interactions through atoms and any combination thereof. At least one linking group B includes a hydrogen acceptor (A), a hydrogen donor (D), and a structural formula (II)

Selected from the group comprising groups having
5. The organic according to claim 1, wherein the hydrogen acceptor (A) and the hydrogen donor (D) are independently selected from the group comprising NH groups and oxygen (O). Compound. At least one of the linking group is a hetero _{atom, COOH, SO 3 H, H} 2 PO 3, NH, NH 2, CO, OH, NHR, NR, COOMe, CONH 2, CONHNH 2, SO 2 NH 2, - Selected from the group consisting of SO ₂ —NH—SO ₂ —NH ₂ , and any combination thereof, wherein the radical R is an alkyl group or an aryl group, and the alkyl group has the general formula C _n H _{2n + 1} — Wherein n is 1 to 23, preferably 1, 2, 3, or 4, wherein the aryl group is selected from the group consisting of phenyl, benzyl and naphthyl. The organic compound according to item. The organic compound according to claim 6, wherein the heteroatom is selected from the group consisting of nitrogen, oxygen, sulfur, and any combination thereof. The organic compound according to claim 1, wherein at least one of the binding groups is a complementary group. The organic compound according to any one of claims 1 to 8, wherein at least one of the linking groups acts as a group that imparts solubility of the organic compound in water or in an organic solvent. At least one group providing solubility of the organic compound in _{water, COOH, SO 3 H, H} 2 PO 3, and selected from the group consisting of any combination thereof, in any one of claims 1 to 9 The organic compound described. At least one group that provides solubility of the organic compound in an organic solvent is selected from the group consisting of CONR ¹ R ² , CONHCONH ₂ , SO ₂ NR ¹ R ² , R ³ , or any combination thereof, wherein , R ¹ , R ² and R ³ are selected from hydrogen, alkyl groups, aryl groups, and any combination thereof, wherein the alkyl group has the general formula C _n H _{2n + 1} — n is 1 to 23, preferably 1, 2, 3, or 4, and the aryl group is selected from the group consisting of phenyl, benzyl, and naphthyl. Compound. 12. The organic compound according to any one of claims 1 to 11, wherein the predominantly planar heterocyclic molecular system is partially or completely conjugated. An organic compound according to any one of claims 1 to 12,
The heterocyclic molecular system is an organic compound having an axis of symmetry of order k (C _k ) perpendicular to the plane of the heterocyclic molecular system, wherein k is an integer of 3 or more. The predominantly planar heterocyclic molecular system has at least one of pyrazine and imidazole rings and has structures 1-4.

The organic compound according to any one of claims 1 to 13, which has a structural formula selected from: 13. The organic compound according to any one of claims 1 to 12, wherein the heterocyclic molecular system has an expanded anisoaxial form with a longitudinal axis. The heterocyclic molecular system has the structure 5-6

Having a structural formula selected from
Wherein portions E and G, O, S, and are independently selected from NR ^4, wherein ^{R 4} is selected from H, _NH 2, OH, organic compound according to claim 15. The said heterocyclic molecular system is an oligomer comprising at least one of imidazole and benzimidazole cycle, and at least one of said imidazole and benzimidazole cycle is capable of forming a hydrogen bond. The organic compound as described in any one of -12,15. The heterocyclic molecular system has the structure 7-15

Having a structural formula selected from
18. The organic compound according to claim 17, wherein n is a number within the range of 1-5. 1H, 1′H-2,2′-bibenzimidazole derivatives, 2,2′-bi-1,3-benzoxazole derivatives, and 2,2′-bi-1,3-benzoxazole derivatives The organic compound according to any one of claims 1 to 12, 15 selected from a list comprising derivatives. Structure 16-34

20. An organic compound according to claim 19 having a structural formula selected from: _{-CH 3, -C 2 H 5,} -NO 2, -Cl, -Br, -F, -CF 3, -CN, -NCS, -OH, -OCH 3, -OC 2 H 5, -OCOCH 3, _{-OCN, -SCN, -NH 2, -NHCOCH} 3, and further comprising at least one additional substituent selected from the group consisting of -CONH _2, organic according to any one of claims 1 to 20 Compound. A substrate having a front surface and a back surface, and at least one solid layer on the surface of the substrate, wherein the solid layer has the structural formula (III)

Wherein Het is a predominantly planar heterocyclic molecular system having hydrophilicity,
B is a linking group,
p is 3, 4, 5, 6, 7, or 8,
S is a molecular group that provides solubility in organic compounds,
m is O, 1, 2, 3, 4, 5, 6, 7, or 8,
X ^{_{is, H +, NH 4 +,}} NH (C 2 H 5) 3 +, NH (CH 3) 3 +, NH (C 3 H 7) 3 +, Na +, K +, Li +, Cs +, A counter ion selected from the group consisting of Ba ²⁺ , Ca ²⁺ , Mg ²⁺ , Sr ²⁺ , La ³⁺ , Zn ²⁺ , Zr ⁴⁺ , Ce ³⁺ , Y ³⁺ , Yb ³⁺ , Gd ³⁺ , and any combination thereof,
t is the number of counter ions)
At least one organic compound
Here, the plane of the heterocyclic molecular system is oriented mainly parallel to the plane of the substrate, and the solid layer is transparent to electromagnetic radiation in the visible spectral range of 400-700 nm, Optical film. 23. The optical film of claim 22, wherein the linking group provides formation through non-covalent chemical bonding of flat non-axial axes particles oriented in the plane of the substrate surface, mainly in a solid layer. . The non-covalent chemical bonds include single hydrogen bonds, dipole interactions, cation-pi interactions, van der Waals interactions, coordination bonds, ionic bonds, ionic dipole interactions, multiple hydrogen bonds, heterogeneous bonds. 24. The optical film of claim 23, independently selected from the group consisting of atom-mediated interactions, and any combination thereof. The organic compound includes a hydrogen acceptor (A), a hydrogen donor (D), and a structural formula (II).

Having at least one linking group selected from the group consisting of:
The optical film according to any one of claims 22 to 24, wherein the hydrogen acceptor (A) and the hydrogen donor (D) are independently selected from a list containing NH groups and oxygen (O). . The bonding group is a heteroatom, COOH, SO ₃ H, H ₂ PO ₃ , NH, NH ₂ , CO, OH, NHR, NR, COOMe, CONH ₂ , CONHNH ₂ , SO ₂ NH ₂ , —SO ₂ —NH. -SO ₂ -NH _2, and are selected from any combination thereof, the radical R in the formula is an alkyl group or an aryl group, the alkyl group has the formula _C n _{H 2n + 1} - have,
26. Here, n is 1 to 23, preferably 1, 2, 3 or 4, and the aryl group is selected from the group consisting of phenyl, benzyl and naphthyl. Optical film. 27. The optical film of claim 26, wherein the heteroatoms are selected from nitrogen, oxygen, sulfur, and any combination thereof. 28. The optical film according to any one of claims 22 to 27, wherein at least one binding group is a complementary group. The organic compound _{is, -CH 3, -C 2 H 5} , -NO 2, -Cl, -Br, -F, -CF 3, -CN, -NCS, -OH, -OCH 3, -OC 2 H 5 29, further comprising at least one additional substituent selected from the group consisting of: —OCOCH ₃ , —OCN, —SCN, —NH ₂ , —NHCOCH ₃ , and —CONH _2. An optical film according to item. 30. The optical film according to any one of claims 22 to 29, wherein the solid layer is substantially insoluble in water. 31. An optical film according to any one of claims 22 to 30, wherein the predominantly planar heterocyclic molecular system is partially or completely conjugated. Wherein the heterocyclic molecular system has a symmetry axis of order k (C _k) which forms the normal to the heterocyclic molecular system of the plane, where k is an integer of 3 or greater, claim 22 The optical film as described in any one of -31. The predominantly planar heterocyclic molecular system has at least one of a pyrazine and an imidazole ring and has structures 1-4.

The optical film according to claim 32, having the structural formula: 32. The optical film according to any one of claims 22 to 31, wherein the heterocyclic molecular system has an enlarged non-equal axis configuration with a longitudinal axis. The heterocyclic molecular system has the structure 5-6

Having a structural formula selected from
Wherein the E and G moieties are independently selected from a list comprising O, S, NR ⁴ , wherein R ⁴ is selected from a list comprising H, NH ₂ , OH. The optical film described in 1. 23. The heterocyclic molecular system is an oligomer comprising at least one of an imidazole and a benzimidazole cycle, and at least one of the imidazole and the benzimidazole cycle can form a hydrogen bond. The optical film as described in any one of -31,34. The heterocyclic molecular system has the structure 7-15

37. The optical film of claim 36, having a structural formula selected from: wherein n is a number in the range of 1-5. The organic compound is a derivative of 1H, 1′H-2,2′-bibenzimidazole, a derivative of 2,2′-bi-1,3-benzoxazole, and 2,2′-bi-1,3. 36. The optical film according to any one of claims 22 to 31, 34, 35 selected from derivatives of benzoxazole. The organic compound has structures 16-34.

40. The optical film of claim 38, having a structural formula selected from: 40. An optical film according to any one of claims 34 to 39, wherein the longitudinal axis of the heterocyclic molecular system has a substantially isotropic alignment in the substrate plane. 40. An optical film according to any one of claims 34 to 39, wherein the longitudinal axis of the heterocyclic molecular system has a substantially anisotropic alignment in the substrate plane. The solid layer generally has two refractive indices (nx and ny) corresponding to two mutually perpendicular directions in the plane of the substrate surface and one refractive index (nz) normal to the substrate surface. 42. The optical film according to any one of claims 22 to 41, wherein the refractive index of the uniaxial retardation layer conforms to the following condition: nx = ny> nz. The solid layer generally has two refractive indices (nx and ny) corresponding to one refractive index (nz) normal to the substrate surface and two mutually perpendicular directions in the plane of the substrate surface. 42. The optical film according to any one of claims 22 to 31, 34 to 39, and 41, wherein the refractive index is in accordance with the following condition: nx> ny> nz. 44. The optical film according to any one of claims 22 to 43, wherein the substrate is made of a polymer. The optical film according to any one of claims 22 to 43, wherein the substrate is made of glass. The optical film according to any one of claims 22 to 45, further comprising an antireflection coating or an antiflushing coating on the back surface of the substrate. 47. The optical film according to any one of claims 22 to 46, wherein the substrate is transparent to electromagnetic radiation in the visible spectral range. The optical film according to claim 47, wherein a transmission coefficient of the substrate in the visible spectrum region is 90% or more. 49. The optical film according to any one of claims 22 to 48, further comprising a planarizing transparent layer on the front surface of the substrate. The optical film according to any one of claims 22 to 45 and 47 to 49, further comprising a reflective layer on the back surface of the substrate. The optical film according to any one of claims 22 to 45, 49, wherein the substrate is a regular reflective or diffusive reflective material. The optical film according to any one of claims 22 to 45, 49, wherein the substrate is a reflective polarizer. 53. The optical film according to any one of claims 22 to 52, further comprising a substantially transparent adhesive layer applied over the solid layer. 54. The optical film of claim 53, further comprising a protective coating provided on the transparent adhesive layer. Comprising two or more solid layers,
55. The two or more solid layers comprise different organic compounds of structural formula (III) that compensate for at least one difference in refractive index (nx, ny, or nz) in two adjacent layers. The optical film as described in any one. 56. The optical film according to any one of claims 22 to 55, wherein the solid layer is partially or completely a crystalline layer. a) Structural formula (I)

Wherein Het is a predominantly planar heterocyclic molecular system having hydrophilicity,
B is a linking group,
p is 3, 4, 5, 6, 7, or 8,
S is a molecular group that gives the solubility of organic compounds,
m is 0, 1, 2, 3, 4, 5, 6, 7, or 8;
(At least a portion of the heterocyclic molecular system is capable of horizontally forming non-equal particles in solution, resulting from the interaction of the side of the linking group by non-covalent chemical bonding)
Preparing a solution of the organic compound or salt thereof;
b) The liquid layer is substantially transparent to electromagnetic radiation in the visible spectral range from 400 to 700 nm, and flat non-equiaxial particles and heterocyclic molecular systems are formed by non-covalent chemical bonds. Applying a liquid layer of the solution to the substrate, due to the interaction of the side surfaces of the binding groups, they bind to each other and are primarily oriented on the plane of the substrate;
c) A method for producing an optical film, comprising a step of drying to form a solid layer. 58. The method of claim 57, wherein the predominantly planar heterocyclic molecular system is partially or fully conjugated. _{-CH 3, -C 2 H 5,} -NO 2, -Cl, -Br, -F, -CF 3, -CN, -NCS, -OH, -OCH 3, -OC 2 H 5, -OCOCH 3, _{-OCN, -SCN, -NH 2, -NHCOCH} 3, and further comprising at least one additional substituent selected from -CONH _2, the method of claim 57 or 58. The linking group includes a hydrogen acceptor (A), a hydrogen donor (D), and a structural formula (II).

60. Any one of claims 57 to 59, wherein the hydrogen acceptor (A) and the hydrogen donor (D) are independently selected from NH groups and oxygen (O). The method described in 1. At least one of the bonding groups is a heteroatom, COOH, SO ₃ H, H ₂ PO ₃ , NH, NH ₂ , CO, OH, NHR, NR, COOMe, CONH ₂ , CONHNH ₂ , SO ₂ NH ₂ , − Selected from SO ₂ —NH—SO ₂ —NH ₂ , and any combination thereof, wherein the radical R is an alkyl or aryl group;
The alkyl group has the general formula C _n H _{2n + 1} —, where n is 1 to 23, preferably 1, 2, 3, or 4, and the aryl group consists of phenyl, benzyl, and naphthyl. 61. A method according to any one of claims 57-60, selected from the group. 62. The method of claim 61, wherein the heteroatom is selected from nitrogen, oxygen, sulfur, and any combination thereof. 63. The method according to any one of claims 57 to 62, wherein at least one of the binding groups is a complementary group. 58. The heterocyclic molecular system has an axis of symmetry of order k (C _k ) perpendicular to the plane of the heterocyclic molecular system, where k is an integer greater than or equal to 3. 64. The method according to any one of -63. The predominantly planar heterocyclic molecular system has a pyrazine and / or imidazole ring and has structures 1-4.

65. The method of claim 64, having the structural formula: 64. A method according to any one of claims 57 to 63, wherein the heterocyclic molecular system has an expanded anisoaxial form with a longitudinal axis. The heterocyclic molecular system has the structure 5-6

Having a structural formula selected from
Wherein the E and G moieties are independently selected from a list comprising O, S, and NR ⁴ , wherein R ⁴ is selected from a list comprising H, NH ₂ , OH; The method described. 58. The heterocyclic molecular system is an oligomer comprising at least one of an imidazole and a benzimidazole cycle, and at least one of the imidazole and the benzimidazole cycle is capable of forming a hydrogen bond. 64. The method according to any one of -63. The heterocyclic molecular system has the structure 7-15

Having a structural formula selected from
69. The method of claim 68, wherein n is a number in the range of 1-5. The organic compound is a derivative of 1H, 1′H-2,2′-bibenzimidazole, a derivative of 2,2′-bi-1,3-benzoxazole, and 2,2′-bi-1,3. 64. The method according to any one of claims 57 to 63, wherein the method is selected from derivatives of benzoxazole. Structure 16-34

72. The method of claim 70, having a structural formula selected from: The non-covalent chemical bonds include single hydrogen bonds, dipole interactions, cation-pi interactions, van der Waals interactions, coordination bonds, ionic bonds, ionic dipole interactions, multiple hydrogen bonds, heterogeneous bonds. 72. The method according to any one of claims 57 to 71, selected from atom-mediated interactions and any combination thereof. 73. The method of any one of claims 57 to 72, wherein the liquid layer further comprises a solvent selected from water, water miscible solvents, and any combination thereof. 74. The method of claim 73, wherein the water miscible solvent is selected from dimethyl sulfoxide, dimethylformamide, acetone, acetylacetone, liquid amine, aqueous amine solution, alcohol, and any combination thereof. 75. A method according to any one of claims 57 to 74, wherein the amount of solvent is controlled to provide the liquid layer viscosity necessary for applying the liquid layer by hydrodynamic flow. The method of claim 75, wherein the viscosity of the liquid layer does not exceed 2 Pa · s. 77. A method according to any one of claims 57 to 76, wherein the drying step is performed in a stream of air. 78. A method according to any one of claims 57 to 77, further comprising a pretreatment step prior to application on the substrate. 79. The method of claim 78, wherein the pretreatment comprises rendering the surface of the substrate hydrophilic. The method according to claim 78 or 79, further comprising providing a planarizing layer in the pretreatment. H ⁺ , Ba ²⁺ , Ca ²⁺ , Mg ²⁺ , Sr ²⁺ , La ³⁺ , Zn ²⁺ , Zr ⁴⁺ , Ce
^{3+, Y 3+, Yb 3+,} Gd 3+, and further comprising a post-treatment step with a solution of any water-soluble inorganic salt having a cation selected from any combination thereof, any of claims 57 to 80 one The method according to item. 82. The method of claim 81, wherein the step of applying the liquid layer to the substrate and the post-processing step are performed simultaneously. The method according to claim 81 or 82, wherein the drying step and the post-treatment step are performed simultaneously. 83. A method according to claim 81 or 82, wherein the post-treatment step is performed after the drying. 85. A method according to any one of claims 57 to 84, wherein the solution is an isotropic solution. 85. A method according to any one of claims 57 to 84, wherein the solution is a lyotropic liquid crystal solution. The method according to any one of claims 57 to 84, wherein the application is performed using a gel. 85. A method according to any one of claims 57 to 84, wherein the application is done using a viscous liquid phase. The step of applying and the step of drying are repeated periodically,
Performing the alignment operation of overlapping the liquid layer on the substrate on the liquid layer on the substrate and performing the alignment operation after or simultaneously with the step of applying the liquid layer to the substrate;
The organic compound in the liquid layer absorbs electromagnetic radiation in the UV spectral range, at least one wavelength sub-range selected independently, which is the same or different from that used in the previous cycle. 89. A method according to any one of claims 57 to 88. The step of applying and the step of drying are repeated periodically,
Performing an operation of aligning the liquid layer on the substrate on the liquid layer on the substrate after the step of applying the liquid layer on the substrate or simultaneously with the step;
The organic compound in the liquid layer is different from that used in the previous cycle, and at least one of the refractive indices (nx, ny, or nz) is different between two adjacent layers. The method according to one item. Structural formula (IV)

(Where q + l = 0, 1, 2, 3 or 4,
q ′ + I ′ = 0, 1, 2, 3, or 4,
The moieties E and G are independently selected from a list containing O, S, NR ⁴ , where R ⁴ is selected from a list containing H, NH ₂ , OH;
R ⁵ , R ′ ⁵ , R ⁶ and R ′ ⁶ are —COOH, —COMe, —CO ₂ Me, —CONH ₂ , —CONHNH ₂ , —SO ₃ H, —SO ₂ NH ₂ , —SO ₂ —NH. Independently selected from —SO ₂ —NH ₂ )
A method for synthesizing a 2,2′-bibenzheteroazole derivative represented by
a) reacting a component of formula (V) with a component selected from structures (VII) and (VIII);
b) reacting the compound obtained in the previous step with the component of chemical formula (VI),

Wherein the solvent is selected from AcOH, DMF, MeOH, EtOH, and mixtures thereof, a method for synthesizing a 2,2′-bibenzheteroazole derivative. A method for synthesizing a 2,2′-bibenzheteroazole derivative represented by structural formula (IV ′), comprising:

(Where q + l = 0, 1, 2, 3 or 4,
Part E is selected from a list containing O, S, NR ⁴ , where R ⁴ is selected from a list containing H, NH ₂ , OH, and R ⁵ , R ⁶ are —COOH, —COMe, —CO _{2 Me, -CONH 2, -CONHNH 2} , -SO 3 H, -SO 2 NH 2, are independently selected from _{-SO 2 -NH-SO 2 -NH 2} )
a) reacting a component of formula (V) with a component selected from structures (VII) and (VIII);

(B) stirring the mixture,
Wherein the solvent is selected from AcOH, DMF, MeOH, EtOH, and mixtures thereof, a method for synthesizing a 2,2′-bibenzheteroazole derivative represented by Structural Formula (IV ′). The mixture further comprises a step of treating with HCl after treatment with Et 3 _N, the step of the processing is performed to a stirred steps and simultaneously or thereafter, the method according to claim 92. Structural formula (IV)

(Where q + l = 0, 1, 2, 3 or 4,
q ′ + I ′ = 0, 1, 2, 3 or 4,
Parts E and G are independently selected from the list containing O, S, NR ⁴
Here, R ⁴ is selected from a list including H, NH ₂ , and OH, and R ⁵ , R ′ ⁵ , R ⁶ , and R ′ ⁶ are —COOH, —COMe, —CO ₂ Me, —CONH ₂ , —CONHNH. _{2, -SO 3 H, -SO 2} NH 2, are independently selected from _{-SO 2 -NH-SO 2 -NH 2} )
2,2′-bibenzheteroazole derivative. Structure 16-34

95. The 2,2′-bibenzheteroazole derivative according to claim 94, having the structural formula: Tricarboxy-5,11,17-trimethyl-11,17-dihydro-5H-bisbenzidiimidazo represented by the structural formula (IX) [1 ′, 2 ′: 3, 4; 1 ″, 2 ″: 5, 6] A method of synthesizing [1,3,5] triazino [1,2-a] benzimidazole-6,12,18-triium bromide,

a) Bromination and methylation of 1H-benzimidazole-6-carboxylic acid to give 2-bromo-1-methyl-1H-benzimidazole-5 (6) -carboxylic acid;
b) a step of condensing 2-bromo-1-methyl-1H-benzimidazole-5 (6) -carboxylic acid obtained in step (a). Bisbenzimidoazo [1 ′, 2 ′: 3,4]; 1 ″, 2 ″: 5,6] [1,3,5] triazino [1,2-a] benz represented by the structural formula (X) A method of synthesizing imidazole-tricarboxylic acid, comprising:

a) preparing methyl 3,4-diaminobenzoate dihydrochloride consisting of bubbling hydrogen chloride through a solution of 3,4-diaminobenzoic acid in methanol;
b) Preparation of methyl 2-oxo-2,3-dihydro-1H-benzimidazole-5-carboxylate by condensation of methyl 3,4-diaminobenzoate dihydrochloride from step (a) with urea Process,
c) Methyl 2-oxo-2,3-dihydro-1H-benzimidazole-5-carboxylate from step (b) is converted to methyl 2-chloro-1H-benzimidazole- by treatment with hydrogen chloride and phosphorus oxychloride. Converting to 5 (6) -carboxylate;
d) Trimerization of the methyl 2-chloro-1H-benzimidazole-5 (6) -carboxylate obtained from step (c) by trimethylbisbenzimidazo [1 ′, 2 ′: 3,4]; 1 ″, 2 ″: 5,6] [1,3,5] triazino [1,2-a] benzimidazole tricarboxylate;
e) Trimethylbisbenzimidazo [1 ', 2': 3,4; 1 ", 2": 5,6] [1,3,5] triazino [1,2-a] benzimidazole from step (d) And alkali-hydrolyzing the methyl ester of the tricarboxylate to obtain the product (X).

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